KR100776457B1 - Polymerizable polyoxyalkylene monoalkylether derivatives, and preparation process thereof - Google Patents

Abstract

The present invention relates to a polymerizable polyoxyalkylene monoalkyl ether derivative using a high-purity polyoxyalkylene monoalkyl ether containing no divalent alcohol compound and a method for producing the same. When the maximum refractive index maximum point on the chromatogram and the shortest distance of the baseline are L, the peak area S ₁ from the elution start point to the fastest elution time at which the refractive index intensity on the chromatogram becomes L / 3 and from the elution start point The ratio of the peak area S ₀ to the maximum refractive index maximum point satisfies S ₁ / S ₀ ≤ 0.15, when the polyoxyalkylene monoalkyl ether and the alkylene oxide are added to the alcohol, The solvent Wi (g) of moisture Ci (ppm) was added to the reaction vessel of V (ml), and when the moisture of the solvent removed after washing was Cf (ppm), Wi x (Cf-Ci) / V ≦ 10 Polyoxy Killen by screen etherified or ester using a monoalkyl ether as a raw material to prepare a polymerizable polyoxyalkylene monoalkyl ether derivative having a specific structure.

Description

Polymerizable polyoxyalkylene monoalkylether derivatives, and preparation process

1 is a model diagram of a chromatogram obtained by gel permeation chromatography of polyoxyalkylene monoalkyl ether.

2 is a chromatogram of polyoxyethylene monomethyl ether of Example 1 of the present invention.

3 is a chromatogram of polyoxyethylene monomethyl ether of Example 2 of the present invention.

4 is a chromatogram of a conventional polyoxyethylene monomethyl ether of Comparative Example 1

5 is a chromatogram of commercial polyoxyethylene monomethyl ether of Comparative Example 2;

6 is a chromatogram of polyoxyethylene monomethyl ether of Example 7 of the present invention.

7 is a chromatogram of polyoxypropylene monostearyl ether of Example 8 of the present invention.

8 is a chromatogram of polyoxypropyleneoxybutylene monobutyl ether of Example 9 of the present invention.

9 is a chromatogram of polyoxyethyleneoxypropylene monomethyl ether of Example 10 of the present invention.

10 is a chromatogram of a conventional polyoxyethylene monomethyl ether of Comparative Example 3

11 is a chromatogram of a conventional polyoxyethylene monomethyl ether of Comparative Example 4

The present invention relates to a polymerizable polyoxyalkylene monoalkyl ether derivative and a method for producing the derivative. More specifically, the present invention relates to a polymerizable polyoxyalkylene monoalkyl ether derivative using a high purity polyoxyalkylene monoalkyl ether containing no dihydric alcohol compound and a method for producing the same.

In recent years, polymerizable polyoxyalkylene monoalkyl ether derivatives have been developed, and polymers having them as monomers and copolymers with other monomers have been developed. However, among polymers using a polymerizable polyoxyalkylene monoalkyl ether as a monomer, there is a case where a polymer having a molecular weight distribution larger than that of the original target is produced, or gelation occurs during the polymerization reaction. The performance of the polymer can not be obtained. As one of the reasons for such a phenomenon, the polymerizable polyoxyalkylene monoalkyl ether derivative contains a bifunctional polymerizable polyalkylene glycol derivative as a by-product, and the bifunctional polymerizable polyalkylene glycol The crosslinking reaction derived from a derivative can be considered.

In order to solve the above problems, a polymerizable polyoxyalkylene monoalkyl ether derivative which does not contain a bifunctional polymerizable polyalkylene glycol derivative as a byproduct may be used as a monomer. For example, a target polymerizable by using a compound having a polymerizable functional group and capable of adding an alkylene oxide as a raw material, adding an alkylene oxide to this, and then reacting the alkyl compound with a hydroxyl group at the terminal. Polyoxyalkylene monoalkyl ether derivative can be obtained. However, under reaction conditions in which an alkylene oxide is added to a compound having a polymerizable functional group, side reactions such as transition of the polymerizable functional group are likely to proceed, and side reactions such as polymerization of the compound having a polymerizable functional group are likely to proceed. Even under the reaction conditions of alkyl etherification, side reactions such as polymerization and decomposition of ester sites are likely to proceed, so that a compound different from the intended compound is often obtained. Therefore, in order to obtain a polymerizable polyoxyalkylene monoalkyl ether derivative, a method of introducing a polymerizable functional group using polyoxyalkylene monoalkyl ether as a raw material is generally used.

The bifunctional polymerizable polyalkylene glycol derivative that is a by-product of the polymerizable polyoxyalkylene monoalkyl ether derivative is a by-product in the polyoxyalkylene monoalkyl ether which is a raw material of the polymerizable polyoxyalkylene monoalkyl ether derivative. It is due to the polyalkylene glycol contained. In other words, when a polymerizable functional group is introduced from a polyoxyalkylene monoalkyl ether containing polyalkylene glycol as a by-product as a raw material, the polymerizable functional group is introduced into the hydroxyl group moiety, and thus the monofunctional polymerization originally intended. This is because a polymerizable polyalkylene glycol derivative having two polymerizable functional groups is formed at both ends of a molecule derived from polyalkylene glycol as a by-product, together with the polyoxyalkylene monoalkyl ether derivative. Thus, in order to obtain a polymerizable polyoxyalkylene monoalkyl ether derivative containing no polymerizable polyalkylene glycol derivative having two polymerizable functional groups, a polyoxyalkylene mono containing no polyalkylene glycol as a byproduct What is necessary is just to use alkyl ether as a raw material.

Polyoxyalkylene monoalkyl ethers are prepared by using monohydric alcohol compounds as starting materials and by directly adding alkylene oxide in the presence of an alkali or an acid catalyst, but it is known that a plurality of by-products are produced depending on the production conditions. (Japan, Oshima Yoshihiko, Mizutani Toshiyasu, Painting Engineering, Vol. 22, pp. 397-403, 1987). For example, when an alkylene oxide is added to a monohydric alcohol compound using an alkali metal or alkaline earth hydroxide as a catalyst, or when an alkylene oxide addition reaction is performed while water is present in the reaction vessel, The water molecule and the alkylene oxide react to form a bifunctional alkylene glycol, and an alkylene oxide is added to the produced alkylene glycol. As a result, polyalkylene glycol which is a dihydric alcohol compound is produced as a by-product simultaneously with polyoxyalkylene monoalkyl ether which is a monovalent alcohol compound. It is not easy to selectively separate only polyoxyalkylene monoalkyl ether from polyoxyalkylene monoalkyl ether in which such by-products coexist, and it is very difficult to process in large quantities. In addition, quantification of the polyalkylene glycol contained in the polyoxyalkylene monoalkyl ether is often difficult, and it is difficult to determine whether it is preferable as a raw material of the polymerizable polyoxyalkylene monoalkyl ether derivative. Of course, it is also difficult to quantify the bifunctional polymerizable polyalkylene glycol derivative contained in the polymerizable polyoxyalkylene monoalkyl ether derivative using these raw materials.

An object of the present invention is to provide a polymerizable polyoxyalkylene monoalkyl ether derivative having a high purity polyoxyalkylene monoalkyl ether containing almost no dihydric alcohol compound and a method for producing the derivative. will be.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, when the polyoxyalkylene monoalkyl ether is a monohydric alcohol compound, the polyalkylene glycol is a dihydric alcohol compound, and the alkylene oxide was added in the system in which they coexist. In this case, the theoretical number of alkylene oxides that can be added to polyalkylene glycol theoretically doubles to that of polyoxyalkylene monoalkyl ether. As a result of earnest examination, the specific distribution in the chromatogram of gel permeation chromatography is shown. A polymerizable polyoxyalkylene monoalkyl ether derivative having a polyoxyalkylene monoalkyl ether having a raw material and having a polymerizable functional group introduced therein has less obstacles derived from a bifunctional polymerizable polyalkylene glycol derivative. It discovered that the present invention was completed based on this knowledge. That is, the present invention,

(1) The following formula [1]:

R ¹ O (AO) n H ...... [1]

(Wherein R ¹ is a hydrocarbon group of ¹ to 18 carbon atoms, AO is an oxyalkylene group of 2 to 4 carbon atoms, AO is at least one species, and when AO is at least two species, the additional form thereof is in a random shape) Or in the form of a block, n is from 5 to 500 in terms of the average molar number of the oxyalkylene group), and SHODEX GPC SYSTEM-11 as a GPC system and SHODEX RI-71 as a differential refraction system. Three continuous SHODEX KF804Ls were used as a column, the column temperature was 40 ° C, and tetrahydrofuran was used as the developing solvent, and the sample solution 0.1 mL / min of the developing solvent was used at a flow rate of 0.1% by weight. In gel permeation chromatography obtained by injecting ml, the start point of elution when the maximum refractive index intensity maximum on the chromatogram expressed by the refractive index intensity and the elution time obtained using the differential refractive index meter and the shortest distance of the baseline are L. Ugh To the refractive index from the intensity of the chromatogram L / 3 to the peak area of the fastest eluting time for the S ₁ and the elution of the refractive index up to the maximum point strength of the peak area from the start point S ₀ ratio of formula (A):

S ₁ / S ₀ ≤0.15 ..... (A)

A polymerizable polyoxyalkylene monoalkyl ether derivative represented by the following formula [2] or formula [3]: using as a raw material a polyoxyalkylene monoalkyl ether represented by formula [1] that satisfies:

R ¹ O (AO) nR ² ...... [2]

R ¹ O (AO) nR ³ ......... [3]

(Wherein, R ¹ , AO and n have the meaning as defined in the formula [1], R ² is an unsaturated hydrocarbon group of 3 to 4 carbon atoms, R ³ is acryloyl group or meta Chloroyl group);

(2) the following formula [1]:

R ¹ O (AO) n H ...... [1]

(Wherein R ¹ is a hydrocarbon group of ¹ to 18 carbon atoms, AO is an oxyalkylene group of 2 to 4 carbon atoms, AO is at least one species, and when AO is at least two species, the additional form thereof is in a random shape) Or in the form of a block, n is from 5 to 500 in terms of the average molar number of the oxyalkylene group), and SHODEX GPC SYSTEM-11 as a GPC system and SHODEX RI-71 as a differential refraction system. Three continuous SHODEX KF804Ls were used as a column, the column temperature was 40 ° C, and tetrahydrofuran was used as the developing solvent, and the sample solution 0.1 mL / min of the developing solvent was used at a flow rate of 0.1% by weight. In gel permeation chromatography obtained by injecting ml, the start point of elution when the maximum refractive index intensity maximum on the chromatogram expressed by the refractive index intensity and the elution time obtained using the differential refractive index meter and the shortest distance of the baseline are L. Ugh To the refractive index from the intensity of the chromatogram L / 3 to the peak area of the fastest eluting time for the S ₁ and the elution of the refractive index up to the maximum point strength of the peak area from the start point S ₀ ratio of formula (A):

S ₁ / S ₀ ≤0.15 ..... (A)

When the polyoxyalkylene monoalkyl ether represented by the formula [1] satisfying the above is prepared by addition polymerization of a C 2 to C 4 alkylene oxide to a monohydric alcohol, moisture in a reaction vessel having a volume of V (ml) When the solvent Wi (g) of Ci (ppm) was added, the solvent was washed by stirring, and the moisture of the solvent removed was Cf (ppm), the following formula (B):

delete

Moisture in reaction vessel = Wi × (Cf-Ci) / V≤10 ...... (B)

By adjusting the moisture in the container so as to obtain a polyoxyalkylene monoalkyl ether represented by the above formula [1], the polyoxyalkylene monoalkyl ether represented by the obtained formula [1] is used as a raw material, and the formula By etherifying the polyoxyalkylene monoalkyl ether represented by [1], a polymerizable polyoxyalkylene monoalkyl ether derivative represented by the following formula [2] is obtained or polyoxyalkyl represented by the formula [1] A method for producing a polymerizable polyoxyalkylene monoalkyl ether derivative, characterized by obtaining a polymerizable polyoxyalkylene monoalkyl ether derivative represented by the following formula [3] by esterifying ene monoalkyl ether:

R ¹ O (AO) nR ² ...... [2]

R ¹ O (AO) nR ³ ...... [3]

(Wherein, R ¹ , AO and n have the meaning as defined in the formula [1], R ² is an unsaturated hydrocarbon group of 3 to 4 carbon atoms, R ³ is acryloyl group or meta Chloroyl group);

(3) The polymerizable polyoxyalkylene monoalkyl ether derivative is formula [2]:

R ¹ O (AO) nR ² ...... [2]

Wherein R ¹ , AO and n have the same meanings as defined in the formula [1], and R ² is an unsaturated hydrocarbon group having 3 to 4 carbon atoms. 1) a polymerizable polyoxyalkylene monoalkyl ether derivative of a substrate;

(4) The polymerizable polyoxyalkylene monoalkyl ether derivative is represented by the following formula [3]:

R ¹ O (AO) nR ³ ......... [3]

Wherein R ¹ , AO and n have the same meanings as defined in the above formula [1], and R ³ is an acryloyl group or a methacryloyl group. (1) base polymerizable polyoxyalkylene monoalkyl ether derivatives;

(5) Provides a homopolymer having a molecular weight of 1,000 to 300,000 obtained by polymerizing a polymerizable polyoxyalkylene monoalkyl ether derivative represented by formula [3] described in the above (4).

Polyoxyalkylene monoalkyl ether of this invention is following formula [1]:

R ¹ O (AO) nH ... [1]

It is a compound represented by. In formula [1], R <^1> is a C1-C18 hydrocarbon group, AO is a C2-C4 oxyalkylene group, AO is 1 or more types, When AO is 2 or more types, the addition form is random It is a shape or block shape, n is 5-500 in average added mole number of an oxyalkylene group.

In formula [1], as a C1-C18 hydrocarbon group represented by R <^1> , For example, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, an isobutyl group, sec-butyl group, tert- Butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group , Heptadecyl group, octadecyl group, cyclohexyl group, phenyl group, benzyl group and the like. In these, a C1-C4 hydrocarbon group is more preferable.

In Formula [1], an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxytetramethylene group etc. are mentioned as a C2-C4 oxyalkylene group represented by AO, for example. Among these, an oxyethylene group, an oxypropylene group, and an oxybutylene group are more preferable. In Formula [1], when AO is 1 or more types, when AO is 2 or more types of oxyalkylene group, the addition form is random form or a block form, and n is 5-5 in average added mole number of an oxyalkylene group. 500, More preferably, it is 10-300. When n is less than 5, there exists a possibility that the dispersing agent obtained using the said polyoxyalkylene monoalkyl ether as a starting material may not express sufficient dispersing performance. When n exceeds 500, a viscosity may become high and handling may become difficult.

The polyoxyalkylene monoalkyl ether of the present invention, in gel permeation chromatography, shows the maximum refractive index maximum point on the chromatogram expressed by the refractive index intensity and the elution time obtained using a differential refractive index meter and the shortest distance of the baseline. When L is used, the ratio of the peak area S ₁ from the elution start point to the fastest elution time at which the refractive index intensity on the chromatogram becomes L / 3 and the peak area S ₀ from the elution start point to the maximum refractive index maximum point is obtained.

S ₁ / S ₀ ≤0.15 ... (A)

Satisfies. However, only peaks derived from polyoxyalkylene alkyl ethers except peaks resulting from developing solvents used in gel permeation chromatography or similar peaks caused by baseline shaking caused by used columns or apparatuses are calculated.

1 is a model diagram of a chromatogram obtained by gel permeation chromatography of polyoxyalkylene monoalkyl ether, the horizontal axis represents the elution time, and the vertical axis represents the refractive index strength obtained using a differential refractive index meter. When a sample solution is purchased and developed by gel permeation chromatography, elution starts from the highest molecular weight molecule at elution start point A, and the elution curve increases with increasing refractive index strength. Thereafter, the elution curve decreases past the refractive index maximum point where the refractive index intensity is maximum. If there are many impurities contained in the high molecular weight side or the low molecular weight side, the refractive index maximum point may appear in addition to the maximum refractive index maximum point. The shortest distance between the maximum refractive index intensity maximum point P and the baseline is obtained, and this is referred to as L. L / 3 is calculated based on L obtained, and the fastest dissolution time B for which the refractive index intensity becomes L / 3 is obtained. The peak area from the elution start point A to the maximum refractive index intensity maximum point P is S ₀ , and the peak area from the elution start point A to the fastest dissolution time B at which the refractive index intensity is L / 3 is S ₁ . The polyoxyalkylene monoalkyl ether of the present invention, the ratio of S ₁ and S _0, S ₁ / S ₀ is 0.15 or less, more preferably 0.12 or less. When S ₁ / S ₀ exceeds 0.15, the content of polyalkylene glycol in the polyoxyalkylene monoalkyl ether is high, and the dispersant obtained by using the polyoxyalkylene monoalkyl ether as a starting material expresses sufficient dispersing performance. There is a fear that you can not.

Polyoxyalkylene monoalkyl ether, polymerized by this as a raw material introducing polymerizable functional groups polyoxyalkylene monoalkyl ether derivative, and a polymer obtained by polymerizing the derivative, that is a homopolymer or copolymer, S ₁ / S As the value of ₀ increases, an increase in the viscosity derived from the bifunctional polymerizable polyalkylene glycol derivative and the like can be observed. When S ₁ / S ₀ exceeds 0.15, when the polymer is used as a dispersant, There is a concern that the dispersion performance may not be sufficiently expressed. However, as S ₁ / S ₀ decreases, an increase in the viscosity derived from the bifunctional polymerizable polyalkylene glycol derivative is difficult to occur, and when S ₁ / S ₀ is 0.15 or less, more preferably 0.12, When a polymer is used as a dispersant, the outstanding performance which should be inherent is exhibited.

In the present invention, the peak area S ₀ And gel permeation chromatography for obtaining peak area S ₁ , but there is no particular limitation, for example, using SHODEX GPC SYSTEM-11 as a GPC system and SHODEX RI-71 as a differential refractometer, and using three consecutive SHODEX KF804L as columns. It can be carried out by mounting, the column temperature to 40 ℃, using tetrahydrofuran as the developing solvent. The developing solvent was flowed at a flow rate of 1 ml / min, 0.1 ml of sample solution with 0.1 wt% sample concentration was injected, and a chromatogram expressed by refractive index intensity and elution time was obtained using a BORWIN GPC calculation program. have.

In the polyoxyalkylene monoalkyl ether of the present invention, when addition polymerization of a C 2-4 alkylene oxide to a monovalent alcohol, the solvent Wi (g) of water Ci (ppm) is added to the reaction container having an internal volume of V (ml). ), And after stirring and washing the solvent, the moisture of the solvent removed is Cf (ppm).

Moisture in reaction vessel = Wi × (Cf-Ci) / V≤10 ... (B)

By satisfy | filling, it can manufacture easily. The moisture in the reaction vessel is 10 or less, more preferably 8 or less, as shown in formula (B).

In the reaction vessel for adding the alkylene oxide, a solvent obtained by previously determining the moisture by the Kaal Fisher method or the like is placed. There is no restriction | limiting in particular in the solvent used, For example, acetone, acetonitrile, etc. are mentioned. The reaction vessel is sealed, and solvent washing in the reaction vessel is performed under normal pressure or pressure under a temperature condition below the boiling point or above the boiling point of the solvent, as necessary. After washing the solvent, the added solvent is carefully taken out, and the water contained in the solvent after washing is measured by the Kaiser Fischer method or the like. Reaction vessel using formula (B) from the internal volume V (ml) of the reaction vessel, the weight Wi (g) of the added solvent, the water Ci (ppm) of the solvent before washing, and the water Cf (ppm) of the solvent after washing. Moisture inside can be obtained.

S ₁ / S ₀ is less than or equal to 0.15 polyoxyalkylene monoalkyl ether of the present invention can be produced by as described below, the surface of, e. Before the reaction, the reaction vessel is washed with a relatively low boiling water-soluble solvent such as methanol, ethanol, isopropanol, acetone, methyl ethyl ketone, acetonitrile, or azeotropic solvent with water such as benzene and toluene. It is dried for 1 hour or more under the conditions of 50 to 150 ° C and 100 Torr or less, and the moisture in the reaction vessel is removed out of the system. Subsequently, a solvent is put in a reaction vessel, and the solvent is washed by stirring. The amount of solvent used for solvent cleaning and the moisture of the solvent before and after washing were measured, and the moisture in the reaction vessel was obtained from the formula (B), and it was confirmed that the moisture in the reaction vessel was 10 or less.

It is preferable that the monohydric alcohol compound which is a starting raw material does not contain much moisture. When the monohydric alcohol compound as a starting material can be distilled without azeotroping with water, reflux is carried out by adding a desiccant such as sodium, potassium, sodium hydroxide or magnesium, and then distilled to remove water and alkali in the reaction vessel. It is added together with an alkali catalyst which removes hydroxides of metals and alkaline earth metals. When adding a raw alcohol or an alkali catalyst to the reaction vessel, care should be taken not to add extreme moisture.

When starting materials have a high boiling point of monohydric alcohol compounds, and when distillation is difficult, a solvent which is azeotropic with water such as toluene is added to the reaction vessel together with monohydric alcohol as a raw material, and it is 50 to 150 ° C under a dry nitrogen gas atmosphere. , And the water contained in the monohydric alcohol which is a raw material can be removed by performing the pressure reduction process for 1 hour or more on the conditions of 200 Torr or less, and removing the added solvent. In addition, an alkali catalyst for removing hydroxides of alkali metals and alkaline earth metals is added so as not to add extreme moisture, and the reaction vessel is pressurized under a dry nitrogen gas atmosphere, and then dried alkylene oxide is 50 to 150. It is added continuously at ℃ and added polymerization. Moreover, it is preferable not to contain moisture as much as the C2-C4 alkylene oxide which addition-reacts with the monohydric alcohol compound which is a starting raw material. Of course, when adding a C2-C4 alkylene oxide into a reaction container, it is also most important to be careful not to add the extreme moisture.

As an alkali catalyst which removes the alkali metal and alkali earth metal hydroxide used as a catalyst of the addition reaction of an alkylene oxide, For example, sodium, potassium, sodium potassium amalgam, sodium hydride, sodium methoxy, potassium methoxide, sodium Ethoxide, potassium ethoxide, etc. are mentioned. Moreover, the methanol solution of sodium methoxide, the ethanol solution of sodium ethoxide, etc. can also be used.

In addition to the alkali catalyst, Lewis acid catalysts such as boron trifluoride and tin tetrachloride are used for the addition reaction of the alkylene oxide. However, when an acid catalyst is used to obtain a high molecular weight compound, such as 1,4-dioxane The cyclic monomer and the cyclic polyether are by-produced, which may make it difficult to obtain a compound having the desired purity.

A first aspect of the polymerizable polyoxyalkylene monoalkyl ether derivative of the present invention is the following formula [2]:

R ¹ O (AO) nR ² ... [2]

It is a compound represented by. In formula [2], R <^1> is a C1-C18 hydrocarbon group, R <^2> is a C2-C4 unsaturated hydrocarbon group, AO is a C2-C4 oxyalkylene group, AO is 1 or more types, When AO is 2 or more types, the addition form is a random form or a block form, and n is 5-500 in average added mole number of an oxyalkylene group.

In formula [2], as a C1-C18 hydrocarbon group represented by R <^1> , For example, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, an isobutyl group, sec-butyl group, tert- Butyl, pentyl, isopentyl, neopentyl, hexyl, heptyl, octyl, nonyl decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, Heptadecyl group, an octadecyl group, a cyclohexyl group, a phenyl group, benzyl group, etc. are mentioned. In these, a C1-C4 hydrocarbon group is more preferable.

In formula [2], as the unsaturated hydrocarbon group having 2 to 4 carbon atoms represented by R ^2, for example, a vinyl group, an allyl group, such as isopropenyl, 1-propenyl group, a metal group, a 3-butenyl group Can be mentioned. Among these, an unsaturated hydrocarbon group having 3 to 4 carbon atoms is preferable, and especially the allyl group and the metalyl group are easy to be introduced into the compound represented by Formula [1], and have a moderate degree of polymerization.

In Formula [2], an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxytetramethylene group etc. are mentioned as a C2-C4 oxyalkylene group represented by AO. In Formula [2], AO is 1 or more types, and when AO is 2 or more types of oxyalkylene groups, the addition form is a random form or a block form. Moreover, n is 5-500 in the average added mole number of an oxyalkylene group, More preferably, it is 10-300. If n is less than 5, there exists a possibility that the dispersing agent containing the polymer of a polymerizable polyoxyalkylene monoalkyl ether derivative may not express sufficient dispersing performance. When n exceeds 500, there exists a possibility that a viscosity may become high and handling may become difficult.

The polymerizable polyoxyalkylene monoalkyl ether derivative represented by formula [2] of the present invention is a chromatogram obtained by gel permeation chromatography,

S ₁ / S ₀ ≤0.15 ... (A)

It manufactures using the polyoxyalkylene monoalkyl ether represented by Formula [1] which satisfy | fills. There is no restriction | limiting in particular in the method of introduce | transducing the unsaturated hydrocarbon group represented by R <^2> into the polyoxyalkylene monoalkyl ether represented by Formula [1], For example, sodium hydroxide and potassium hydroxide in a polyoxyalkylene monoalkyl ether. Alkali metal hydroxides, such as these, can be added and it can obtain by etherification reaction with monohalogenated unsaturated hydrocarbons, such as allyl chloride, allyl bromide, allyl iodide, metall chloride, and metall bromide.

The 2nd aspect of the polymerizable polyoxyalkylene monoalkyl ether derivative of this invention is a following formula [3]:

R ¹ O (AO) nR ³ ... [3]

It is a compound represented by. In formula [3], R <^1> is a C1-C18 hydrocarbon group, R <^3> is acryloyl group or methacryloyl group, AO is a C2-C4 oxyalkylene group, AO is 1 or more types And, when two or more AOs are used, the addition type thereof is in a random form or in a block form, and n is 5-500 in average molar number of oxyalkylene groups.

In formula [3], as a C1-C18 hydrocarbon group represented by R <^1> , For example, a methyl group, an ethyl group, a propyl group, isopropyl group, a butyl group, an isobutyl group, sec-butyl group, tert- Butyl group, pentyl group, isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group , Heptadecyl group, octadecyl group, cyclohexyl group, phenyl group, benzyl group and the like. Among these, it is more preferable than a C1-C4 hydrocarbon group.

In formula [3], an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxytetramethylene group etc. are mentioned as a C2-C4 oxyalkylene group represented by AO. In Formula [3], when AO is 1 or more types and AO is 2 or more types of oxyalkylene groups, the addition form is a random form or a block form. Moreover, n is 5-500 in the average added mole number of an oxyalkylene group, More preferably, it is 10-300. When n is less than 5, there exists a possibility that the dispersing agent containing the polymer of a polymerizable polyoxyalkylene monoalkyl ether derivative may not express sufficient dispersibility. When n exceeds 500, a viscosity may become high and handling may become difficult.

The polymerizable polyoxyalkylene monoalkyl ether derivative represented by formula [3] of the present invention is a chromatogram obtained by gel permeation chromatography,

S ₁ / S ₀ ≤0.15 ... (A)

It manufactures using the polyoxyalkylene monoalkyl ether represented by Formula [1] which satisfy | fills. There is no restriction | limiting in particular in the method of introduce | transducing the acryloyl group or methacryloyl group represented by R <^3> into the polyoxyalkylene monoalkyl ether represented by Formula [1], For example, to polyoxyalkylene monoalkyl ether A catalyst such as p-toluenesulfonic acid monohydrate can be added, and it can be obtained by esterification with acrylic acid or methacrylic acid. A catalyst such as sodium methoxide is added to a polyoxyalkylene monoalkyl ether to give methyl acrylate. Or by transesterification with alkyl acrylate or alkyl methacrylate, such as methyl methacrylate, or by reaction with polyoxyalkylene monoalkyl ether and acrylic acid chloride or methacrylic acid chloride. Or obtained by the reaction of a polyoxyalkylene monoalkyl ether with an acrylic anhydride or methacrylic anhydride There is also.

The polymer of this invention is a copolymer obtained by copolymerizing 5 to 95 mol% of the polymerizable polyoxyalkylene monoalkyl ether derivatives represented by Formula [2], and 95-5 mol% of monomers copolymerizable with this, or a formula [ 5 to 95 mol% of a polymerizable polyoxyalkylene monoalkyl ether derivative represented by 3] as a monomer or a polymerizable polyoxyalkylene monoalkyl ether derivative represented by formula [3], copolymerizable with this It is a copolymer obtained by copolymerizing 95-5 mol% of monomers. The homopolymer of the polymerizable polyoxyalkylene monoalkyl ether derivative represented by Formula [3] has a molecular weight of 1,000-300,000, More preferably, it is 5,000-100,000. The homopolymer may be one kind or a mixture of two or more kinds of polymerizable polyoxyalkylene monoalkyl ether derivatives represented by formula [3].

A copolymer obtained by copolymerizing 5 to 95 mol% of the polymerizable polyoxyalkylene monoalkylether derivative represented by formula [2] with 95 to 5 mol% of copolymerizable monomers thereof, or represented by formula [3] The molecular weight of the copolymer obtained by copolymerizing 5 to 95 mol% of polymerizable polyoxyalkylene monoalkyl ether derivatives and 95 to 5% mol% of monomers copolymerizable therewith is 500 to 100,000, and more preferably 1,000 to 50,000. to be. If the molecular weight of the copolymer is less than 500, the dispersant containing the copolymer may not express sufficient dispersing performance. When the molecular weight of a copolymer exceeds 100,000, there exists a possibility that a viscosity may become high and handling becomes difficult.

Polymeric polyester of the formula [2] of the present invention polyoxyalkylene copolymers of monoalkyl ether derivative has the formula [2] R ² of the polymerizable polyoxyalkylene monoalkyl ether derivative represented by the carbon number of 3 to It is more preferable that it is an unsaturated hydrocarbon group of 4. Since an unsaturated hydrocarbon group of 3 to 4 carbon atoms has a suitable degree of polymerization, the polymer can be easily produced.

Examples of the copolymerizable monomers include unsaturated monocarboxylic acids and salts thereof such as acrylic acid, methacrylic acid and crotonic acid, unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid and salts thereof, methyl Polymeric aromatics, such as alkyl acrylates, such as acrylate, ethyl acrylate, and butyl acrylate, alkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate, styrene, p-styrene sulfonic acid, and indene Olefin, such as an unsaturated compound, isobutylene, and isoprene, maleimide, such as N-phenylmaleimide and N-cyclohexyl maleimide, other acrylamides, maleic anhydride, a maleic acid alkyl ester, vinyl acetate, acrylo Nitrile, allylsulfonic acid, metalylsulfonic acid, salts thereof, and the like. These monomers can be used individually by 1 type, or can also be used in combination of 2 or more type. Among these, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid and salts thereof can be used suitably, and acrylic acid, methacrylic acid, maleic acid and maleic anhydride can be particularly suitably used.

In the present invention, the homopolymer of the polymerizable polyoxyalkylene monoalkyl ether derivative represented by formula [3] and the polymerizable polyoxyalkylene monoalkyl ether derivative represented by formula [2] or formula [3] 5 to The molecular weight of the copolymer obtained by copolymerizing 95% and 95-5 mol% of copolymerizable monomers with this is the value measured by gel permeation chromatography (henceforth called GPC), and is a weight average molecular weight of polyethylene glycol conversion. .

There is no restriction | limiting in particular in the manufacturing method of the polymer of this invention, The polymerizable polyoxyalkylene monoalkyl ether derivative represented by Formula [3] is independent, or is polymerizable represented by Formula [2] or Formula [3]. The monomer copolymerizable with a polyoxyalkylene monoalkyl ether derivative can be solution-polymerized at the same time in an organic solvent or an aqueous solvent, or may be bulk-polymerized with a non-solvent. Moreover, as a polymerization initiator used for a polymerization reaction, in the case of an aqueous solvent, for example, hydroperoxides, such as tert- butyl hydroperoxide, persulfates, such as sodium persulfate, potassium persulfate, ammonium persulfate, etc. A water-soluble polymerization initiator can be mentioned. When the polymerization is carried out in an organic solvent or a solvent-free system, for example, peroxides such as benzoyl peroxide and di-tert-butyl peroxide, azo initiators such as 2,2'-azobisisobutyronitrile, and the like. Can be mentioned. These polymerization initiators can be used individually by 1 type, or can also be used in combination of 2 or more type.

The dispersing agent of this invention is a homopolymer of the polymeric polyoxyalkylene monoalkyl ether derivative represented by Formula [3], or the polymeric polyoxyalkylene monoalkyl ether represented by Formula [2] or Formula [3]. It contains 5 to 95 mol% of derivatives and the copolymer of 95-5 mol% of monomers copolymerizable with this. 5 to 95 mol% of a homopolymer of the polymerizable polyoxyalkylene monoalkyl ether derivative represented by formula [3] and a polymerizable polyoxyalkylene monoalkyl ether derivative represented by formula [2] or formula [3], The copolymer of this monomer 95-5% copolymerizable with this exhibits the outstanding dispersibility as a component of a dispersing agent. The copolymer to be contained in the dispersant is a copolymer of 30 to 70 mol% of the polymerizable polyoxyalkylene monoalkyl ether derivative represented by formula [2] or [3] and a monomer of 70 to 30 mol% copolymerizable with this. It is more preferable.

There is no restriction | limiting in particular in the form of the dispersing agent of this invention, For example, a polymer can be used independently, a polymer can also be used as an aqueous solution or an organic solvent solution, or the chemical agent, such as an antifoamer, is added to the solution of a copolymer further, for example. It can also be used. There is no restriction | limiting in particular in the usage-amount of the dispersing agent of this invention, For example, with respect to the solid to be disperse | distributed, it adds so that a polymer may be 0.01 to 10 weight%, Preferably it is 0.1 to 5 weight%, and to a high-liquid dispersion system, It is possible to remarkably improve the dispersion state of the solid particles and the sedimentation inhibiting effect.

Although the dispersing agent of this invention can be used as various dispersing agents, Preferably it can be used for ceramic use, can form the slurry of high density | concentration of an inorganic powder, and it can be used for coating use, disperse | distributing a pigment to a primary particle in an excipient, A stable suspension can be formed. Moreover, it can be used for cement use, and can improve the fluidity | liquidity and fluid holding | maintenance property of mortar and concrete, and can improve high strength, high durability, and workability. The dispersant of the present invention is particularly useful as a dispersant for inorganic powders and a dispersant for cement.

[ Example ]

Hereinafter, the present invention will be described in more detail with reference to Examples.

Example  One

The stainless steel 5 liter (4,890 ml) internal pressure reactor equipped with a thermometer, a pressure gauge, a safety valve, a nitrogen gas blowing pipe, a stirrer, a vacuum exhaust pipe, a cooling coil, and a steam jacket was washed with water, and the water in the reaction vessel was washed with water. The mixture was removed with a dry nitrogen gas, and then dried under reduced pressure at 50 to 100 Torr for 15 minutes while supplying steam to the steam jacket. After the completion of the water washing step, the reaction mixture was returned to normal pressure, cooled to room temperature, 2 liters of methanol was added thereto, and stirred in a nitrogen gas atmosphere at 0.05 to 0.1 MPa and 70 to 75 ° C for 30 minutes, and the reaction vessel was washed with methanol. Methanol was discarded, dry nitrogen gas was blown into the reaction vessel, steam was supplied to the steam jacket, and dried under reduced pressure at 50 to 100 Torr for 1 hour.

After cooling to room temperature, 2,060 g of a commercially available dehydrated acetonitrile (46 ppm was measured by Kaal Fisher's method) was added from a tube into which nitrogen gas was blown. After pressurizing with 0.05 Mpa by dry nitrogen gas, it stirred for 15 minutes. Subsequently, the acetonitrile was carefully removed and 2,001 g of acetonitrile was recovered. The moisture of the acetonitrile removed was found to be 60 ppm by the Kaiser Fischer method. The moisture in the reaction vessel calculated from the formula (B) was 5.7.

Acetonitrile remaining in the reaction vessel was removed by dry nitrogen gas, steam was supplied to the steam jacket, and dried under reduced pressure at 50 to 100 Torr for 1 hour. After the reaction apparatus was cooled to 30 ° C. or lower, 27 g of dehydrated methanol having a water content of 18 ppm and 5 g of sodium methoxide were added thereto, and the reaction vessel was replaced with nitrogen gas. After heating up to 90 degreeC, 1,890g of ethylene oxides were continuously pressurized under stirring from the nitrogen-gas-injected tube on the conditions of 90-100 degreeC and 0.6 Mpa or less. After completion of the ethylene oxide addition, the mixture was reacted at 90 to 100 ° C for 2 hours. Next, after cooling to 80 degreeC, the pressure reduction process was performed at 75-85 degreeC and 50-100 Torr for 1 hour, blowing in nitrogen gas. 200 g of the reaction product was taken out, neutralized with 1N hydrochloric acid, dehydrated and filtered in a nitrogen gas atmosphere, and the reaction product was measured by gel permeation chromatography (GPC).

GPC is equipped with SHODEX GPC SYSTEM-11 as a system, SHODEX RI-71 as a differential refractometer, and 3 SHODEX KF804L as columns, and a column temperature of 40 ° C and tetrahydrofuran as a developing solvent at a flow rate of 1 ml / min. 0.1 mL of 0.1 wt% tetrahydrofuran solution of the obtained reactant was poured, and a chromatogram represented by refractive index intensity and elution time was obtained using a BORWIN GPC calculation program. 2 is the chromatogram obtained. Ask the S ₁ / S ₀ was obtained from the chromatogram and found to 0.137.

54 g of potassium hydroxide was added to the remaining reactants, and the reaction vessel was replaced with nitrogen gas, followed by a reduced pressure treatment at 80 to 90 DEG C and 50 to 100 Torr for 1 hour. After cooling to 60 degreeC, 75 g of allyl chlorides were pressurized in the system by nitrogen gas from the tube which nitrogen gas is blown, and it was made to react at 80-90 degreeC and 0.2-0.3 Mpa for 4 hours. The reaction was neutralized with 6N hydrochloric acid, then dehydrated under reduced pressure, and the generated salt was removed by filtration to obtain polyoxyethylene monomethyl monoallyl ether (a).

Example  2

Washing and drying were performed similarly to Example 1 using the pressure-resistant reaction apparatus similar to Example 1. After cooling to room temperature, 1,750 g of commercially available dehydrated acetone (42 ppm was measured by Kaal Fisher's method) was added from a tube into which nitrogen gas was blown. Pressurized with dry nitrogen gas to 0.05 Mpa, and stirred for 15 minutes. Subsequently, acetone was carefully removed and 1,744 g of acetone was recovered. The moisture of the acetone taken out was 59 ppm by the Kael Fisher method. The moisture in the reaction vessel calculated from the formula (B) was 6.1.

Acetone remaining in the reaction vessel was removed by dry nitrogen gas, steam was supplied to the steam jacket, and dried under reduced pressure at 50 to 100 Torr for 1 hour. After cooling to room temperature, 19 g of a methanol solution of sodium methoxide (Kawaken Fine Chemical Co., Ltd., SM-28, 28% by weight of sodium methoxide) was added thereto, and the reaction vessel was replaced with nitrogen gas. After heating up to 90 degreeC, 2,845 g of ethylene oxides were continuously pressurized under stirring from the nitrogen-gas blowing pipe on 90-100 degreeC and the conditions of 0.6 Mpa or less. After completion of the addition of ethylene oxide, the mixture was reacted at 90 to 100 ° C for 2 hours. Next, after cooling to 80 degreeC, the pressure reduction process was performed at 75-85 degreeC and 50-100 Torr for 1 hour, blowing in nitrogen gas.

After 195 g of the reaction product was taken out and neutralized with 1N hydrochloric acid, dehydration and filtration were performed in a nitrogen gas atmosphere, and the reaction product obtained was measured by GPC. 3 is a chromatogram obtained. Obtaining a S ₁ / S ₀ was obtained from the chromatogram and was 0.112.

34 g of potassium hydroxide was added to the remaining reactants, and the resultant was replaced with nitrogen gas, followed by a reduced pressure treatment at 80 to 90 ° C. and 50 to 100 Torr for 1 hour. After cooling to 65 degreeC, 73 g of allyl bromide were press-injected into the system by nitrogen gas from the tube which nitrogen gas is blown, and it was made to react at 80-90 degreeC and 0.2-0.3 Mpa for 4 hours. The reaction was neutralized with 6N hydrochloric acid, dehydrated under reduced pressure, and the generated salt was removed by filtration to obtain polyoxyethylene monomethyl monoallyl ether (b).

Example  3

Washing and drying were performed similarly to Example 1 using the pressure-resistant reaction apparatus similar to Example 1. After cooling to room temperature, 1,789 g of commercially available dehydrated acetone (42 ppm was measured by the Kael Fisher method) was added from a tube into which nitrogen gas was blown. After pressurizing with 0.05 Mpa by dry nitrogen gas, it stirred for 15 minutes. Subsequently, the acetone was carefully removed and 1,783 g of acetone was recovered. The moisture of the acetone taken out was 61ppm when it was calculated | required by the Kaiser Fischer method. The moisture in the reaction vessel calculated from the formula (B) was 7.0.

Acetone remaining in the reaction vessel was removed by dry nitrogen gas, steam was supplied to the steam jacket, and dried under reduced pressure at 50 to 100 Torr for 1 hour. After cooling to room temperature, 550 g of stearyl alcohol was added thereto, and the reaction vessel was replaced with nitrogen gas. After heating up to 110 degreeC, dehydration was performed at 105-115 degreeC under reduced pressure of 100 Torr or less, blowing in nitrogen gas into a reaction container. It cooled to 70 degreeC after completion | finish of dehydration, and some 17g was taken out and it was 37 ppm when water content was calculated | required by the Kael Fisher method. 1 g of methoxide was added to sodium, and the reaction vessel was replaced with nitrogen gas. Next, after heating up to 80 degreeC, 1,200g of propylene oxides were continuously pressurized under stirring from 90 to 100 degreeC and the pipe which nitrogen gas is blown in 0.6 Mpa or less. After completion of the propylene oxide addition, the mixture was reacted at 90 to 100 ° C for 2 hours. Next, after cooling to 80 degreeC, the pressure reduction process was performed at 75-85 degreeC and 50-100 Torr for 1 hour, blowing in nitrogen gas.

After 103 g of the reaction product was taken out and neutralized with 1N hydrochloric acid, dehydration and filtration were carried out in a nitrogen gas atmosphere, and the reaction product obtained was measured by GPC. Obtaining a S ₁ / S ₀ was obtained from the chromatogram, it was 0.110.

120 g of potassium hydroxide was added to the remaining reaction product, and the resultant was replaced with nitrogen gas, followed by reduced pressure treatment at 80 to 90 DEG C and 50 to 100 Torr. After cooling to 60 degreeC, 168 g of allyl chlorides were press-injected in the system by nitrogen gas from the tube which nitrogen gas is blown, and it was made to react on 80-90 degreeC and the conditions of 0.2-0.3 Mpa for 4 hours. After the reaction was neutralized with 6N hydrochloric acid, dehydration was carried out under reduced pressure, and the generated salt was removed by filtration to obtain polyoxypropylene monostearyl monoallyl ether (c).

Example  4

Washing and drying were performed similarly to Example 1 using the pressure-resistant reaction apparatus similar to Example 1. After cooling to room temperature, 1,912 g of commercially available dehydrated acetonitrile (46 ppm was measured by Kael Fisher's method) was added from a tube into which nitrogen gas was blown. After pressurizing with 0.05 Mpa by dry nitrogen gas, it stirred for 15 minutes. Subsequently, the acetonitrile was carefully removed and 1907 g of acetonitrile was recovered. The moisture of the acetonitrile taken out was 63 ppm by the Kael Fisher method. The moisture in the reaction vessel calculated from the formula (B) was 6.6.

Acetonitrile remaining in the reaction vessel was removed by dry nitrogen gas, steam was supplied to the steam jacket, and dried under reduced pressure at 50 to 100 Torr for 1 hour. After cooling to room temperature, 72 g of n-butanol and 3 g of potassium-tert-butoxide having a water content distilled beforehand were added, and the reaction vessel was replaced with nitrogen gas. After heating up to 80 degreeC, the mixture of 1,030g of ethylene oxides and 1,370g of propylene oxides was continuously pressurized under stirring from 90-100 degreeC and the tube of nitrogen gas blown in 0.6 Mpa or less. After the addition of the mixture of ethylene oxide and propylene oxide was terminated, the mixture was reacted at 90 to 100 ° C for 2 hours. Next, after cooling to 80 degreeC, the pressure reduction process was performed at 75-85 degreeC and 50-100 Torr for 1 hour, blowing in nitrogen gas.

97 g of the reaction product was taken out, neutralized with 1N hydrochloric acid, and then dehydrated and filtered under a nitrogen gas atmosphere. The reaction product was measured by GPC. Obtaining a S ₁ / S ₀ was obtained from the chromatogram, it was 0.110.

62 g of potassium hydroxide was added to the remaining reactants, and the resultant was replaced with nitrogen gas, followed by reduced pressure treatment at 80 to 90 DEG C and 50 to 100 Torr for 1 hour. After cooling to 60 degreeC, 85 g of allyl chlorides were press-injected in the system by nitrogen gas from the tube which nitrogen gas is blown, and it was made to react at 80-90 degreeC and 0.2-0.3 Mpa for 4 hours. After the reaction was neutralized with 6N hydrochloric acid, dehydration was carried out under reduced pressure, and the generated salt was removed by filtration to obtain polyoxyethyleneoxypropylene monobutyl monoallyl ether (d).

Example  5

Washing and drying were performed similarly to Example 1 using the pressure-resistant reaction apparatus similar to Example 1. After cooling to room temperature, 1,544 g of commercially available dehydrated acetonitrile (46 ppm was measured by Kaal Fisher's method) was added from a tube into which nitrogen gas was blown. After pressurizing with 0.05 Mpa by dry nitrogen gas, it stirred for 15 minutes. Subsequently, the acetonitrile was carefully removed, and 1,539 g of acetonitrile was recovered. The moisture of the acetonitrile removed was found to be 66 ppm by the Kaiser Fischer method. The moisture in the reaction vessel computed from Formula (B) was 6.3.

Acetonitrile remaining in the reaction vessel was removed by dry nitrogen gas, steam was supplied to the steam jacket, and dried under reduced pressure at 50 to 100 Torr for 1 hour. After cooling to room temperature, 76 g of a methanol solution of sodium methoxide (Kawaken Fine Chemical Co., Ltd., SM-28, 28% by weight of sodium methoxide) was added, and the reaction system was replaced with nitrogen gas. After heating up to 90 degreeC, 1,860 g of 1, 2- butylene oxides were continuously pressure-added continuously under stirring from the pipe | tube which blows in nitrogen gas at 90-100 degreeC and 0.6 Mpa or less. After completion of the 1,2-butylene oxide addition, the mixture was reacted at 90 to 100 ° C for 3 hours. Next, after cooling to 80 degreeC, the pressure reduction process was performed at 75-85 degreeC and 50-100 Torr for 1 hour, blowing in nitrogen gas.

Moreover, after heating up to 90 degreeC, 530g of ethylene oxides were continuously added under stirring from the tube which nitrogen-gas blows on on the conditions of 90-100 degreeC and 0.6 Mpa or less. After completion of the addition of ethylene oxide, the mixture was reacted at 90 to 100 ° C for 2 hours. Next, after cooling to 80 degreeC, the pressure reduction process was performed at 75-85 degreeC and 50-100 Torr for 1 hour, blowing in nitrogen gas.

After 112 g of the reaction product was taken out and neutralized with 1N hydrochloric acid, dehydration and filtration were carried out in a nitrogen gas atmosphere, and the reaction product obtained was measured by GPC. Obtaining a S ₁ / S ₀ was obtained from the chromatogram, it was 0.081.

134 g of potassium hydroxide was added to the remaining reactants, and the resultant was replaced with nitrogen gas, followed by a reduced pressure treatment at 80 to 90 DEG C and 50 to 100 Torr for 1 hour. After cooling to 65 degreeC, 208 g of metalyl chlorides were press-injected into the system by nitrogen gas from the tube which nitrogen gas is blown, and it was made to react at 80-90 degreeC and 0.2-0.3 Mpa for 4 hours. After the reaction was neutralized with 6N hydrochloric acid, dehydration was carried out under reduced pressure, and the generated salt was removed by filtration to obtain polyoxybutyleneoxyethylene monomethyl monometall ether (e).

Example  6

Washing and drying were performed similarly to Example 1 using the pressure-resistant reaction apparatus similar to Example 1. After cooling to room temperature, 1,982 g of commercially available dehydrated acetonitrile (46 ppm was measured by Kael Fisher's method) was added from a tube into which nitrogen gas was blown. After pressurizing with 0.05 Mpa by dry nitrogen gas, it stirred for 15 minutes. Subsequently, the acetonitrile was carefully removed and 1,974 g of acetonitrile was recovered. The moisture of the acetonitrile taken out was 58 ppm by the Kael Fisher method. The moisture in the reaction container computed from Formula (B) was 4.9.

Acetonitrile remaining in the reaction vessel was removed by dry nitrogen gas, steam was supplied to the steam jacket, and dried under reduced pressure at 50 to 100 Torr for 1 hour. After cooling to room temperature, 61 g of a methanol solution of sodium methoxide [Kawaken Fine Chemical Co., Ltd., SM-28, 28 weight% of sodium methoxide] was added, and the reaction vessel was replaced with nitrogen gas. After heating up to 90 degreeC, 2,420g of ethylene oxides were continuously pressure-added under stirring from the tube which nitrogen-gas is blown on 90-100 degreeC and the conditions of 0.6 Mpa or less. After completion of the addition of ethylene oxide, the mixture was reacted at 90 to 100 ° C for 2 hours. Next, after cooling to 80 degreeC, the pressure reduction process was performed at 75-85 degreeC and 50-100 Torr for 1 hour, blowing in nitrogen gas.

After 200 g of the reaction product was taken out and neutralized with 1N hydrochloric acid, dehydration and filtration were carried out in a nitrogen gas atmosphere, and the reaction product obtained was measured by GPC. Obtaining a S ₁ / S ₀ from the chromatogram obtained eojin, it was 0.092.

108 g of potassium hydroxide was added to the remaining reactants, and the resultant was replaced with nitrogen gas, followed by a reduced pressure treatment at 80 to 90 DEG C and 50 to 100 Torr for 1 hour. After cooling to 65 degreeC, 135 g of allyl chlorides were pressurized in the system by nitrogen gas from the tube which blows nitrogen gas, and it was made to react at 80-90 degreeC and 0.2-0.3 Mpa for 4 hours. After the reaction was neutralized with 6N hydrochloric acid, dehydration was carried out under reduced pressure, and the generated salt was removed by filtration to obtain polyoxyethylene monomethyl monoallyl ether (f).

Comparative example  One

After washing the pressure-resistant reactor similar to Example 1 with water well, the water in the reaction vessel was removed by dry nitrogen gas, and then dried under reduced pressure at 50 to 100 Torr for 15 minutes while supplying steam to the steam jacket. After cooling to room temperature, 1,992 g of commercially available dehydrated acetonitrile of 46 ppm of water, which was the same as that used in Example 1, was added from a tube blown with nitrogen gas, pressurized to 0.05 MPa with dry nitrogen gas, and stirred for 15 minutes. Subsequently, the acetonitrile was carefully removed and 1,986 g of acetonitrile was recovered. The moisture of the acetonitrile removed was found to be 108 ppm by the Kaiser Fischer method. The moisture in the reaction vessel calculated from the formula (B) was 25.3.

After the reactor was cooled to 30 ° C. or lower, 27 g of dehydrated methanol and 5 g of sodium methoxide were added thereto, and the reaction vessel was replaced with nitrogen gas. After heating up to 90 degreeC, on the conditions of 90-100 degreeC and 0.6 Mpa or less, 1,890 g of ethylene oxides were continuously pressurized from the nitrogen-gas blowing tube under stirring. After completion of the addition of ethylene oxide, the reaction was carried out at 90 to 100 ° C for 2 hours. Next, after cooling to 80 degreeC, the pressure reduction process was performed at 75-85 degreeC and 50-100 Torr for 1 hour, blowing in nitrogen gas.

After 200 g of the reaction product was removed and neutralized with 1N hydrochloric acid, dehydration and filtration were carried out in a nitrogen gas atmosphere, and the reaction product obtained was measured by GPC. 4 is a chromatogram obtained. Ask the S ₁ / S ₀ was obtained from the chromatogram and was 0.214.

55 g of potassium hydroxide was added to the remaining reactants, and the resultant was replaced with nitrogen gas, followed by a reduced pressure treatment at 80 to 90 DEG C and 50 to 100 Torr for 1 hour. After cooling to 60 ° C, 77 g of allyl chloride was press-fitted into the system with nitrogen gas from a tube into which nitrogen gas was blown, and reacted at 80 to 90 ° C at 0.2 to 0.3 MPa for 4 hours. The reaction was neutralized with 6N hydrochloric acid, dehydrated under reduced pressure, and the generated salt was removed by filtration to obtain polyoxyethylene monomethyl monoallyl ether (a ').

Comparative example  2

Commercially available polyoxyethylene monomethyl ether (Reagent from Aldrich: Poly (ethylene glycol) methylether: model number 20,251-7, weight average molecular weight, 5,000) was measured by GPC. 5 is a chromatogram obtained. Obtaining a S ₁ / S ₀ was obtained from the chromatogram and found to 0.183.

200 g of the above polyoxyethylene monomethyl ether was added to a 1 L glass pressure reactor, and potassium hydroxide 2.6 g was added and replaced with nitrogen gas, followed by a reduced pressure treatment at 80 to 90 ° C. and 50 to 100 Torr for 1 hour. . After cooling to 60 degreeC, 5.6 g of allyl bromide was press-injected into the system by nitrogen gas from the tube which nitrogen gas was blown, and it was made to react at 80-90 degreeC and 0.2-0.3 Mpa for 5 hours. The reaction was neutralized with 6N hydrochloric acid, dehydrated under reduced pressure, and the generated salt was removed by filtration to obtain polyoxyethylene monomethyl monoallyl ether (b ').

The values of L, S ₀ , S ₁ and S ₁ / S ₀ of the chromatograms of Examples 1 to 6 and Comparative Examples ₁ and 2 are shown in Table 1, and the synthetic conditions and the properties of the obtained compound are shown in Table 2.

L (elution time) L / 3 (Dissolution Time) S ₀ S ₁ S ₀ / S ₁ Example 1 0.0107 (25.142) 0.0036 (24.733) 44.0974 6.0321 0.137 Example 2 0.0129 (23.542) 0.0043 (23.221) 41.1708 4.6299 0.112 Example 3 0.0138 (25.550) 0.0046 (24.957) 39.5182 4.3585 0.110 Example 4 0.0168 (23.642) 0.0056 (23.057) 41.2735 4.5498 0.110 Example 5 0.0111 (24.950) 0.0037 (24.292) 36.8409 2.9797 0.081 Example 6 0.0123 (24.450) 0.0041 (23.897) 44.0926 4.0700 0.092 Comparative Example 1 0.0100 (25.417) 0.0033 (24.967) 49.8518 10.6513 0.214 Comparative Example 2 0.0127 (23.592) 0.0042 (23.264) 44.4713 8.1553 0.183

Example 1 Example 2 Example 3 Example 4 R ¹ methyl methyl Stearyl n-butyl AO EO EO PO EO / PE Wi (g) 2006 1750 1789 1912 Ci (ppm) 46 42 42 46 Cf (ppm) 60 59 61 63 V (m1) 4890 4890 4890 4890 moisture 5.7 6.1 7.0 6.6 Hydroxyl value (KOHmg / g) 27.9 10.1 66.1 23.2 Molecular Weight 2010 5550 850 2420 n 45 126 10 23/23 S ₁ / S ₂ 0.137 0.112 0.110 0.110 R ² Allyl Allyl Allyl Allyl Unsaturation (meq / g) 0.49 0.18 1.17 0.41

Example 5 Example 6 Comparative Example 1 Comparative Example 2 R ¹ methyl methyl methyl methyl AO BO-EO EO EO E Wi (g) 1544 1982 1992 - Ci (ppm) 46 46 46 - Cf (ppm) 66 58 108 - V (m1) 4890 4890 4890 - moisture 6.3 4.9 25.3 - Hydroxyl value (KOHmg / g) 48.4 36.7 27.9 10.2 Molecular Weight 1160 1530 2010 5500 n 12-6 34 45 124 S ₁ / S ₀ 0.081 0.092 0.214 0.183 R ² Metal reel Allyl Allyl Allyl Unsaturation (meq / g) 0.86 0.65 0.49 0.18

EO: ethylene oxide, PO: propylene oxide

BO: 1,2-butylene oxide

EO / PO: Random addition, BO-EO: Block addition

Hydroxyl value: measured in accordance with JIS K 1557 6.4

Unsaturation: measured according to JIS K 1557 6.7

Molecular weight and n are calculated values calculated | required from the hydroxyl value as being monoalkyl ether.

Example  7

Washing and drying were performed similarly to Example 1 using the pressure-resistant reaction apparatus similar to Example 1. After cooling to room temperature, 2,010 g of commercially available dehydrated acetonitrile (51 ppm was measured by Kael Fisher's method) was added from a tube into which nitrogen gas was blown. After pressurizing with 0.05 Mpa by dry nitrogen gas, it stirred for 15 minutes. Subsequently, acetonitrile was carefully removed to recover 2,002 g of acetonitrile. The moisture of the acetonitrile removed was found to be 60 ppm by the Kaiser Fischer method. The moisture in the reaction vessel computed from Formula (B) was 6.2.

Acetonitrile remaining in the reaction vessel was removed by dry nitrogen gas, steam was supplied to the steam jacket, and dried under reduced pressure at 50 to 100 Torr for 1 hour. After the reaction apparatus was cooled to 30 ° C. or lower, 128 g of dehydrated methanol and 27 g of sodium methoxide having 21 ppm of water were added thereto, and the reaction vessel was replaced with nitrogen gas. After heating up to 90 degreeC, 3,640g of ethylene oxides were continuously added under stirring from the tube which nitrogen-gas is blown on the conditions of 90-100 degreeC and 0.6 Mpa or less. After completion of the addition of ethylene oxide, the mixture was reacted at 90 to 100 ° C for 2 hours. Next, after cooling to 80 degreeC, the pressure reduction process was performed at 75-85 degreeC and 50-100 Torr for 1 hour, blowing in nitrogen gas. The reaction was transferred to a 5 L branch flask, quickly neutralized with 1N hydrochloric acid, filtered after dehydration in a nitrogen gas atmosphere, and the reaction product was measured by GPC. 6 is a chromatogram obtained. Obtaining a S ₁ / S ₀ was obtained from the chromatogram and was 0.114.

Into a 5-liter four-necked flask equipped with a stirrer, thermometer, air blowing tube, Dean and Stark tube and Dimroth tube, 1,650 g of reactant was added thereto, and 1,400 g of toluene was added thereto. 115 g of p-toluenesulfonic acid monohydrate and 5 g of hydroquinone were added, it heated up to 50 degreeC, and stirred at 50-60 degreeC for 30 minutes. Next, 206 g of methacrylic acid was added and reacted for 9 hours at 110-120 degreeC, blowing air from the pipe which blows air using an air pump. The reaction was cooled to 60 ° C., transferred to a separatory funnel, and 5N aqueous sodium hydroxide solution was added thereto, shaken well, and the bottom layer was separated after standing. Further, 20 wt% aqueous sodium chloride solution was added thereto, shaken well, and the lower layer generated after standing was separated. 0.1 g of p-methoxyphenol was added to the upper layer, and toluene was removed on 60 degrees C or less under reduced pressure, and polyoxyethylene monomethyl ether methacrylate (g) was obtained.

Example  8

Washing and drying were performed similarly to Example 1 using the pressure-resistant reaction apparatus similar to Example 1. After cooling to room temperature, 2,100 g of commercially available dehydrated acetone (44 ppm was measured by the Kaal Fisher method) was added from a tube into which nitrogen gas was blown. Pressurized with dry nitrogen gas to 0.05 Mpa, and stirred for 15 minutes. Subsequently, acetone was carefully removed and 2,095 g of acetone was recovered. The moisture of the acetone taken out was 59 ppm by the Kael Fisher method. The moisture in the reaction container computed from Formula (B) was 6.4.

Acetone remaining in the reaction vessel was removed by dry nitrogen gas, steam was supplied to the steam jacket, and dried under reduced pressure at 50 to 100 Torr for 1 hour. After cooling to room temperature, 1,100 g of stearyl alcohol was added thereto, and the reaction vessel was replaced with nitrogen gas. After heating up to 110 degreeC, dehydration was performed at 105-115 degreeC under reduced pressure of 100 Torr or less, blowing in nitrogen gas into a reaction container. After completion of the dehydration, the mixture was cooled to 70 ° C, some 19 g was taken out, and the water content was determined by the Car Fischer method to obtain 34 ppm. 2 g of sodium methoxide was added to replace the reaction vessel with nitrogen gas. Subsequently, after heating up to 80 degreeC, 2,870g of propylene oxides were continuously pressurized under stirring from the pipe | tube which blows into nitrogen gas on the conditions of 90-100 degreeC and 0.6 Mpa or less. After completion of the propylene oxide addition, the mixture was reacted at 90 to 100 ° C for 2 hours.

Next, after cooling to 80 degreeC, the pressure reduction process was performed at 75-85 degreeC and 50-100 Torr for 1 hour, blowing in nitrogen gas. A portion of 307 g of the reaction product was transferred to a 0.5 L branch flask, quickly neutralized with 1N hydrochloric acid, filtered after dehydration in a nitrogen gas atmosphere, and the reaction product was measured by GPC. 7 is a chromatogram obtained. Obtaining a S ₁ / S ₀ was obtained from the chromatogram and found to 0.117.

967 g of the remaining reactant was placed in a 3-liter four-necked flask equipped with a stirring device, a thermometer, and an air blowing tube, which was then added to a methanol solution of sodium methoxide [Japan, Kawaken Fine Chemicals, SM-28, Sodium]. 28 g of methoxide] was added, and nitrogen was heated to 110 ° C. under a gas atmosphere, and then methanol was blown at 105 to 110 ° C. under reduced pressure of 100 Torr or less while blowing nitrogen gas into the reaction vessel.

After cooling to 50 ° C., a Leibig tube and a pressure dividing separator were installed, 1,032 g of methyl methacrylate and 0.6 g of t-butylhydroxytoluene were added, and air was blown from the tube blown with an air pump. It was made to react at 75-85 degreeC and 500 Torr for 4 hours, blowing. Then, methyl methacrylate was collect | recovered at 50 Torr or less and 95-105 degreeC. The reaction was cooled to 60 ° C., then transferred to a separatory funnel, an aqueous 85 wt% phosphoric acid solution and a 20 wt% sodium chloride solution were added, shaken well, and the bottom layer generated after standing still was separated. Subsequently, 20 weight% sodium chloride aqueous solution was added, it shaken well, the bottom layer which generate | occur | produced after standing still was isolate | separated, and polyoxypropylene monostearyl ether methacrylate (h) was obtained.

Example  9

Washing and drying were performed similarly to Example 1 using the pressure-resistant reaction apparatus similar to Example 1. After cooling to room temperature, 1,975 g of commercially available dehydrated acetonitrile (51 ppm was measured by Kael Fisher's method) was added from a tube into which nitrogen gas was blown. After pressurizing with 0.05 Mpa by dry nitrogen gas, it stirred for 15 minutes. Subsequently, the acetonitrile was carefully removed and 1,968 g of acetonitrile was recovered. The moisture of the acetonitrile taken out was 65 ppm by the Kael Fisher method. The moisture in the reaction vessel calculated from the formula (B) was 5.7.

Acetonitrile remaining in the reaction vessel was removed by dry nitrogen gas, steam was supplied to the steam jacket, and dried under reduced pressure at 50 to 100 Torr for 1 hour. After cooling to room temperature, 144 g of n-butanol and 6 g of potassium-tert-butoxide having a distilled water content of 26 ppm were added thereto, and the reaction vessel was replaced with nitrogen gas. Next, after heating up to 80 degreeC, 2,416g of propylene oxides were continuously pressurized under stirring from 90 to 100 degreeC and the pipe which nitrogen gas is blown in 0.6 Mpa or less. After completion of the propylene oxide addition, the mixture was reacted at 90 to 100 ° C. for 2 hours, cooled to 80 ° C., and depressurized at 75 to 85 ° C. and 50 to 100 Torr for 1 hour while blowing nitrogen gas. Next, after heating up to 80 degreeC, 588 g of 1, 2- butylene oxides were continuously pressure-added continuously under stirring from the tube which nitrogen gas is blown in 90-100 degreeC and 0.6 Mpa or less. After the completion of the addition of 1,2-butylene oxide, the mixture was reacted at 90 to 100 ° C for 3 hours, cooled to 80 ° C, and depressurized at 75 to 85 ° C and 50 to 100 Torr for 1 hour while blowing nitrogen gas. .

The reaction was transferred to a 5 L branch flask, quickly neutralized with 1N hydrochloric acid, filtered after dehydration in a nitrogen gas atmosphere, and the reaction product was measured by GPC. 8 is the chromatogram obtained. Obtaining a S ₁ / S ₀ from the chromatogram, it was 0.103.

Into a 5-liter four-necked flask equipped with a stirring device, a thermometer, an air blowing tube, a Dean Stark tube, and a dim rod tube, 1,456 g of the reactant was added thereto, 1,200 g of toluene was added thereto, and 46 g of p-toluenesulfonic acid monohydrate. And 6 g of hydroquinones were added, it heated up to 50 degreeC, and stirred at 50-60 degreeC for 30 minutes. Next, 89 g of methacrylic acid was added and reacted at 110-120 degreeC for 12 hours, blowing air from the pipe which blows air using an air pump. The reaction was cooled to 60 ° C., transferred to a separatory funnel, shaken well by adding 5 N aqueous sodium hydroxide solution, and the lower layer generated after standing was separated. Further, 20 wt% aqueous sodium chloride solution was added thereto, shaken well, and the lower layer generated after standing was separated. 0.1 g of p-methoxyphenol was added to the upper layer, and toluene was removed on 60 degrees C or less under reduced pressure, and polyoxypropylene oxybutylene monobutyl ether methacrylate (i) was obtained.

Example  10

Washing and drying were performed similarly to Example 1 using the pressure-resistant reaction apparatus similar to Example 1. After cooling to room temperature, 1,857 g of commercially available dehydrated acetonitrile (51 ppm was measured by Kael Fisher's method) was added from a tube blown with nitrogen gas. After pressurizing with 0.05 Mpa by dry nitrogen gas, it stirred for 15 minutes. Subsequently, the acetonitrile was carefully removed and 1,848 g of acetonitrile was recovered. The moisture of the acetonitrile removed was found to be 68 ppm by the Kaiser Fischer method. The moisture in the reaction vessel computed from Formula (B) was 6.5.

Acetonitrile remaining in the reaction vessel was removed by dry nitrogen gas, steam was supplied to the steam jacket, and dried under reduced pressure at 50 to 100 Torr for 1 hour. After cooling to room temperature, 76 g of a methanol solution of sodium methoxide (Kawaken Fine Chemical Co., Ltd., SM-28, 28% by weight of sodium methoxide) was added, and the reaction system was replaced with nitrogen gas. After heating up to 90 degreeC, the mixture of 2,904 g of ethylene oxides and 1.196 g of propylene oxides was continuously pressurized under stirring from the pipe | tube which blows in nitrogen gas at 90-100 degreeC and 0.6 Mpa or less. After the addition of the mixture of ethylene oxide and propylene oxide was completed, the mixture was reacted at 90 to 100 ° C. for 3 hours, then cooled to 80 ° C., and then depressurized at 75 to 85 ° C. and 50 to 100 Torr for 1 hour while blowing nitrogen gas. Was performed.

The reaction was transferred to a 5 L branch flask, quickly neutralized with 1N hydrochloric acid, filtered after dehydration in a nitrogen gas atmosphere, and the reaction product was measured by GPC. 9 is a chromatogram obtained. Obtaining a S ₁ / S ₀ was obtained from the chromatogram and was 0.124.

Into a 5-liter four-necked flask equipped with a stirring device, a thermometer, an air blowing tube, a Dean Stark tube, and a dim rod tube, 1,415 g of the reactant was added thereto, and 1,500 g of n-hexane was added thereto, and p-toluenesulfonic acid · 1 was added. 53g of hydrate and 6g of hydroquinone were added, it heated up to 40 degreeC, and stirred at 50-60 degreeC for 30 minutes. Next, 66 g of acrylic acid was added and the reaction was carried out at 70 to 75 ° C. for 12 hours while blowing air from a tube through which air was blown using an air pump. After the reaction was cooled to 50 ° C., the reaction mixture was transferred to a separatory funnel, and 5N aqueous sodium hydroxide solution was added thereto, shaken well, and the lower layer generated after standing was separated. Moreover, 20 weight% sodium chloride aqueous solution was added, shaken well, and the lower layer which generate | occur | produced after standing still was isolate | separated. 0.1 g of p-methoxyphenol was added to the upper layer, n-hexane was removed on 50 degreeC or less under reduced pressure, and polyoxyethylene oxypropylene monomethyl ether acrylate (j) was obtained.

Example  11

Washing and drying were performed similarly to Example 1 using the pressure-resistant reaction apparatus similar to Example 1. After cooling to room temperature, 2,206 g of commercially available dehydrated acetone (44 ppm was measured by Kael Fisher's method) was added from a tube blown with nitrogen gas. After pressurizing with 0.05 Mpa by dry nitrogen gas, it stirred for 15 minutes. Subsequently, acetone was carefully removed and 2,197 g of acetone was recovered. The moisture of the acetone taken out was 63 ppm by the Kael Fisher method. The moisture in the reaction vessel calculated from the formula (B) was 8.6.

Acetone remaining in the reaction vessel was removed by dry nitrogen gas, steam was supplied to the steam jacket, and dried under reduced pressure at 50 to 100 Torr for 1 hour. After cooling to room temperature, 46 g of a methanol solution of sodium methoxide (Kawaken Fine Chemical Co., Ltd., SM-28, 28% by weight of sodium methoxide) was added, and the reaction system was replaced with nitrogen gas. After heating up to 90 degreeC, 3,683g of ethylene oxides were continuously pressure-added from 90-100 degreeC and 0.6 Mpa or less in the tube which nitrogen gas was blown under stirring. After completion of the addition of ethylene oxide, the reaction was carried out at 90 to 100 ° C. for 2 hours, and then cooled to 80 ° C., followed by a reduced pressure treatment at 75 to 85 ° C. and 50 to 100 Torr for 1 hour while blowing nitrogen gas.

The reaction was transferred to a 5 L branch flask, quickly neutralized with 1N hydrochloric acid, filtered after dehydration in a nitrogen gas atmosphere, and the reaction product was measured by GPC. Obtaining a S ₁ / S ₀ was obtained from the chromatogram and was 0.119.

Into a 5-liter four-necked flask equipped with a stirring device, a thermometer, an air blowing tube, a Dean Stark tube, and a dim rod tube, 1,477 g of the reactant was added thereto, 1,500 g of toluene was added thereto, and 38 g of p-toluenesulfonic acid monohydrate. And 6 g of hydroquinones were added, it heated up to 50 degreeC, and stirred at 50-60 degreeC for 30 minutes. Next, 60 g of methacrylic acid was added and reacted at 110-120 degreeC for 12 hours, blowing air from the pipe which blows air using an air pump. The reaction was cooled to 60 ° C., transferred to a separatory funnel, and 5N aqueous sodium hydroxide solution was added thereto, shaken well, and the lower layer formed after standing was separated. Further, 20 wt% aqueous sodium chloride solution was added thereto, shaken well, and the lower layer generated after standing was separated. 0.1 g of p-methoxyphenol was added to the upper layer, and toluene was removed on 60 degrees C or less under reduced pressure, and polyoxyethylene monomethyl ether methacrylate (k) was obtained.

Comparative example  3

After washing the pressure-resistant reactor similar to Example 1 with water well, the water in the reaction vessel was removed by dry nitrogen gas, and then dried under reduced pressure at 50 to 100 Torr for 15 minutes while supplying steam to the steam jacket. After cooling to room temperature, 2,004 g of commercially available dehydrated acetonitrile having 51 ppm of moisture, which was the same as that used in Example 7, was added from a tube blown with nitrogen gas, pressurized to 0.05 MPa with dry nitrogen gas, and stirred for 15 minutes. Subsequently, the acetonitrile was carefully removed and 1,997 g of acetonitrile was recovered. The moisture of the acetonitrile taken out was 121 ppm by the Kael Fisher method. The moisture in the reaction vessel computed from Formula (B) was 28.7.

After the reaction apparatus was cooled to 30 ° C. or lower, 128 g of dehydrated methanol and 27 g of sodium methoxide were added thereto, and the reaction vessel was replaced with nitrogen gas. After heating up to 90 degreeC, 3,640g of ethylene oxides were continuously pressurized under the nitrogen gas blowing tube on 90-100 degreeC and the conditions of 0.6 Mpa or less, stirring. After completion of the addition of ethylene oxide, the reaction was carried out at 90 to 100 ° C for 2 hours. Next, after cooling to 80 degreeC, the pressure reduction process was performed at 75-85 degreeC and 50-100 Torr for 1 hour, blowing in nitrogen gas. The reaction was transferred to a 5 L branch flask, quickly neutralized with 1N hydrochloric acid, filtered after dehydration in a nitrogen gas atmosphere, and the reaction product was measured by GPC. 10 is a chromatogram obtained. Obtaining a S ₁ / S ₀ was obtained from the chromatogram and found to 0.156.

Into a 5-liter four-necked flask equipped with a stirrer, a thermometer, an air blowing tube, a Dean Stark tube, and a dim rod tube, 1,650 g of the reactant was added thereto, 1,400 g of toluene was added thereto, and 115 g of p-toluenesulfonic acid monohydrate. And 5 g of hydroquinones were added, it heated up to 50 degreeC, and stirred at 50-60 degreeC for 30 minutes. Next, 206 g of methacrylic acid was added and reacted for 9 hours at 110-120 degreeC, blowing air from the pipe which blows air using an air pump. The reaction was cooled to 60 ° C., transferred to a separatory funnel, and 5N aqueous sodium hydroxide solution was added thereto, shaken well, and the lower layer formed after standing was separated. Further, 20 wt% aqueous sodium chloride solution was added thereto, shaken well, and the lower layer generated after standing was separated. 0.1 g of p-methoxyphenol was added to the upper layer, and toluene was removed on 60 degrees C or less under reduced pressure, and polyoxyethylene monomethyl ether methacrylate (g ') was obtained.

Comparative example  4

After washing the pressure-resistant reactor similar to Example 1 with water well, the water in the reaction vessel was removed by dry nitrogen gas, and then dried under reduced pressure at 50 to 100 Torr for 15 minutes while supplying steam to the steam jacket. After cooling to room temperature, 46 g of a methanol solution of sodium methoxide [Kawaken Fine Chemical Co., Ltd., SM-28, 28% by weight of sodium methoxide] was added, and the reaction system was replaced with nitrogen gas. After heating up to 90 degreeC, 3,683g of ethylene oxides were stirred and added continuously at 90-100 degreeC and 0.6 Mpa or less in the tube which nitrogen gas was blown. After completion of the addition of ethylene oxide, the reaction was carried out at 90 to 100 ° C. for 2 hours, and then cooled to 80 ° C., followed by a reduced pressure treatment at 75 to 85 ° C. and 50 to 100 Torr for 1 hour while blowing nitrogen gas.

The reaction was transferred to a 5 L branch flask, quickly neutralized with 1N hydrochloric acid, filtered after dehydration in a nitrogen gas atmosphere, and the reaction product was measured by GPC. 11 is a chromatogram obtained. Obtaining a S ₁ / S ₀ was obtained from the chromatogram and was 0.195.

Into a 5-liter four-necked flask equipped with a stirring device, a thermometer, an air blowing tube, a Dean Stark tube, and a dim rod tube, 1,477 g of the reactant was added thereto, 1,500 g of toluene was added thereto, and 38 g of p-toluenesulfonic acid monohydrate. And 6 g of hydroquinones were added, it heated up to 50 degreeC, and stirred at 50-60 degreeC for 30 minutes. Next, 60 g of methacrylic acid was added and reacted at 110-120 degreeC for 12 hours, blowing air from the pipe which blows air using an air pump. The reaction was cooled to 60 ° C., transferred to a separatory funnel, and 5N aqueous sodium hydroxide solution was added thereto, shaken well, and the lower layer formed after standing was separated. Further, an aqueous 20 wt% sodium chloride solution was added thereto, shaken well, and the lower layer generated after standing was separated. 0.1 g of p-methoxyphenol was added to the upper layer, and toluene was removed under the reduced pressure of 60 degrees C or less, and polyoxyethylene monomethyl ether methacrylate (k ') was obtained. Examples 7-11 and comparison The values of L, S ₀ , S ₁ and S ₁ / S ₀ of the chromatograms of Examples 3 to 4 are shown in Table 3, and the synthetic conditions and the properties of the obtained compound are shown in Table 4.

L (elution time) L / 3 (Dissolution Time) S ₀ S ₁ S ₁ / S ₀ Example 7 0.0082 (27.358) 0.0027 (26.808) 45.4770 5.2003 0.1144 Example 8 0.0065 (26.983) 0.0022 (26.692) 44.3610 5.1769 0.1167 Example 9 0.0077 (25.792) 0.0026 (25.192) 48.7876 5.0300 0.1030 Example 10 0.0100 (25.558) 0.0033 (25.117) 46.1342 5.7068 0.1237 Example 11 0.0112 (24.783) 0.0037 (24.388) 44.6310 5.2977 0.1187 Comparative Example 3 0.0081 (27.258) 0.0027 (26.692) 47.9631 7,4925 0.1562 Comparative Example 4 0.0099 (24.567) 0.0033 (24.117) 46.3476 9.0365 0.1950

Example 7 Example 8 Example 9 Example 10 Example 11 Comparative Example 3 Comparative Example 4 R ¹ methyl Stearyl n-butyl methyl methyl methyl methyl AO EO PO PO-BO EO / PO EO EO E0 Wi (g) 2010 2100 1975 1857 2206 2004 2210 Ci (ppm) 51 44 51 51 44 51 44 Cf (ppm) 66 59 65 68 63 121 112 V (m1) 4890 4890 4890 4890 4890 4890 4890 moisture 6.3 6.4 5.7 6.5 8.6 28.7 45.8 Hydroxyl value (KOHmg / g) 68.1 58.0 30.8 27.8 19.0 68.0 19.1 Molecular Weight 824 967 1821 2018 2953 825 2937 n 18 12 25-4 32/10 67 18 67 S ₁ / S ₀ 0.114 0117 0.103 0.124 0.119 0.156 0.195 R ² MA MA MA A MA MA MA Saponification Value (KOHmg / g) 61.7 56.5 31.3 28.2 19.5 61.7 19.5 Bromine (mg / 100g) 17.6 14.8 8.0 7.4 5.0 17.5 5.0

EO: ethylene oxide, PO: propylene oxide

BO: 1,2-butylene oxide

PO-BO: block added, EO / PO: random added

MA: methacryloyl group, A: acryloyl group

Hydroxyl value: measured in accordance with JIS K 1557 6.4

Saponification value: measured according to JIS K 0070

Bromine number: measured according to JIS K 2605

Molecular weight and n are calculated values calculated | required from the hydroxyl value as being monoalkyl ether.

Example  12

Into a 1 L four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas blowing tube, and a cooling tube, 500 g of polyoxyethylene monomethyl monoallyl ether (a) obtained in Example 1, 27 g of maleic anhydride, and 200 ml of toluene were placed. The temperature was raised to 60 ° C. under a nitrogen gas atmosphere. Subsequently, 12 g of benzoyl peroxides were added and reacted for 8 hours at 70-75 degreeC under nitrogen gas atmosphere. After completion | finish of reaction, toluene which is a solvent was removed under 90-100 degreeC and pressure reduction, and the reddish brown copolymer (P-a) was obtained. The kinematic viscosity at 100 ° C of the obtained copolymer (P-a) was 251 cSt, and the molecular weight measured by GPC was 20,900.

In addition, as a GPC system, SHODEX GPC SYSTEM-11 and SHODEX R1-71 were used as a differential refractive index meter, and three SHODEX KF-801, KF-803, and KF-804 were continuously mounted as a column. The column temperature was 40 degreeC, 0.05 mol / L sodium nitrate aqueous solution was used as a developing solvent, it flowed at the flow rate of 1 ml / min, and 0.1 ml of sample solutions of 0.1 weight% of sample concentration were injected. Molecular weight is the weight average molecular weight of polyethyleneglycol standard conversion calculated | required based on the chromatogram obtained using the BORWIN GPC calculation program.

Hereinafter, also in Examples 13-14, Examples 17-19, Comparative Examples 5-6, and Comparative Examples 8-9, the measurement was performed on the same conditions.

Example  13

Into a four-necked flask similar to Example 12, 390 g of polyoxyethylene monomethyl monoallyl ether (b) obtained in Example 2, 13 g of maleic acid, 4.4 g of sodium allyl sulfonate, and 400 g of water were added thereto, and the temperature was raised to 30 ° C. These were dissolved. Subsequently, 9.6 g of ammonium persulfate was added and reacted for 18 hours at 60-70 degreeC under nitrogen gas atmosphere, and the aqueous solution of the yellowish-brown copolymer (P-b) was obtained. The kinematic viscosity at 25 degrees C of the aqueous solution of the obtained copolymer was 787 cSt, and it was 49.6 weight% when the polymer concentration of the copolymer aqueous solution was calculated | required from the drying loss after 120 degreeC and 2 hours passed. Moreover, it was 34,700 when the molecular weight of the copolymer obtained by drying was measured by GPC.

Example  14

Into a four-necked flask similar to that of Example 12, 480 g of polyoxyethyleneoxypropylene monobutyl monoallyl ether (d) obtained in Example 4, 4 g of styrene, 23.5 g of maleic anhydride and 300 ml of xylene were placed, and under a nitrogen gas atmosphere, It heated up to 45 degreeC. Subsequently, 1.6 g of 2,2'- azobisisobutyronitrile were added, and it was made to react at 75-80 degreeC under nitrogen gas atmosphere for 8 hours. After completion of the reaction, xylene as a solvent was removed at 90 to 100 ° C. under reduced pressure to obtain a pale yellow copolymer (P-d). The kinematic viscosity at 100 ° C of the obtained copolymer was 205 cSt, and the molecular weight measured by GPC was 23,900.

Comparative example  5

The reaction was carried out in the same manner as in Example 12, except that the polyoxyethylene monomethyl monoallyl ether (a ') obtained in Comparative Example 1 was used instead of the polyoxyethylene monomethyl monoallyl ether (a) obtained in Example 1. And reddish brown copolymer (P-a ') were obtained. The kinematic viscosity at 100 ° C of the obtained copolymer (P-a ') was 283 cSt, and the molecular weight measured by GPC was 26,100.

Comparative example  6

In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a nitrogen gas blowing tube, and a cooling tube, 126 g of polyoxyethylene monomethyl monoallyl ether (b ') obtained in Comparative Example 2, 4.1 g of maleic acid, sodium allyl sulfonate 1.4 g and 129 g of water were added, and it heated up to 30 degreeC, and dissolved them. Subsequently, 3.1 g of ammonium persulfate was added, and the mixture was reacted at 60 to 70 ° C. for 18 hours under a nitrogen gas atmosphere to obtain an aqueous solution of a tan copolymer (P-b '). The kinematic viscosity at 25 degrees C of the aqueous solution of the obtained copolymer was 985 cSt, and it was 49.1 weight% when the polymer concentration of the aqueous solution of copolymer was calculated | required from the drying loss after 120 degreeC and 2 hours passed. Moreover, it was 41,600 when the molecular weight of the copolymer obtained by drying was measured by GPC.

Table 5 shows the compositions of the copolymers obtained in Examples 12-14 and Comparative Examples 5-6.

Copolymer symbol Compound of formula [2] Copolymerizable Monomer sign confiscation compound confiscation Example 12 P-a a 0.25 Maleic anhydride 0.28 Example 13 P-b b 0.07 Sodium allyl sulfonate 0.11 0.03 Example 14 P-d d 0.20 Styrene Maleic Anhydride 0.04 0.24 Comparative Example 5 P-a ' a ' 0.25 Maleic anhydride 0.28 Comparative Example 6 P-b ' b ' 0.02 Sodium allyl sulfonate 0.03 0.01

Example  15

223 g of polyoxyethylene monomethyl ether methacrylate (g) obtained in Example 7, 100 g of water, 300 g of 2-propanol, and thioglycol in a 2-liter four-necked flask equipped with a stirrer, a cooling tube, a nitrogen gas introduction tube, and a thermometer. 10 g of acid and 2 g of potassium persulfate were added thereto, and the mixture was polymerized at 70 to 75 ° C. under a nitrogen gas atmosphere for 6 hours. After completion of the reaction, 2-propanol as a solvent was removed under reduced pressure to obtain an aqueous solution of the polymer. It was 30.3 weight% when the polymer concentration of the polymer aqueous solution was calculated | required from the drying loss after 120 degreeC and 2 hours passed. The kinematic viscosity at 40 degrees C of the obtained polymer aqueous solution was 1,173 cSt, and the molecular weight of the polymer calculated | required by GPC was 63,100.

15 g of the obtained aqueous polymer solution was weighed into a 200 ml Erlenmeyer flask with a common stopper, and 135 g of tetrahydrofuran was added thereto, and the mixture was shaken well. As a result, the solution was transparent.

As a GPC system, SHODEX RI-71 was used as a SHODEX GPC SYSTEM-11 and a differential refractive index meter, and SHODEX KF804L was mounted as a column. The column temperature was 40 degreeC, tetrahydrofuran was flowed at the flow rate of 1 ml / min as a developing solvent, and 0.1 ml of sample solutions of 0.1 weight% of sample concentration were injected. Molecular weight is the weight average molecular weight of polyethyleneglycol standard body conversion calculated | required based on the chromatogram obtained using the BORWIN GPC calculation program.

Also in the following Example 16 and the comparative example 7, it measured on the same conditions.

Example  16

189 g of polyoxypropylene oxybutylene monobutyl ether methacrylate (i) obtained in Example 9, 500 g of 2-propanol, 4 g of α-methylstyrene dimer, and 2 g of benzoyl peroxide were placed in a device similar to that of Example 15. In the atmosphere, the polymerization was carried out at 75 to 80 ° C. for 5 hours. After the completion of the reaction, the polymer concentration of the polymer solution was determined to be 28.2% by weight based on the loss of drying after 2 hours at 120 ° C. The kinematic viscosity at 40 ° C of this polymer solution was 197 cSt, and the molecular weight of the polymer determined by GPC was 53,300.

15 g of the obtained polymer solution was weighed in a 200 ml common stopper flask with a balance, and 135 g of tetrahydrofuran was added thereto, and the mixture was shaken well. As a result, the solution was transparent.

Comparative example  7

A polyoxyethylene monomethyl ether methacrylate (g ') obtained in Example 7 was used in the same manner as in Example 15 except that 223 g of the polyoxyethylene monomethyl ether methacrylate (g') obtained in Comparative Example 3 was used. The reaction was carried out. After completion of the reaction, 2-propanol as a solvent was removed under reduced pressure to obtain an aqueous solution of the polymer. It was 30.5 weight% when the polymer concentration of the polymer aqueous solution was calculated | required from the drying loss after 120 degreeC and 2 hours passed. The kinematic viscosity at 40 degrees C of the obtained polymer aqueous solution was 1,548 cSt, and the molecular weight of the polymer calculated | required by GPC was 76,400.

15 g of the obtained aqueous polymer solution was weighed into a 200 ml Erlenmeyer flask with a common stopper, and 135 g of tetrahydrofuran was added thereto, and the mixture was shaken well. It is assumed that there is a polymer insoluble by crosslinking.

Example  17

54 g of maleic anhydride and 200 g of toluene were placed in a 2-liter four-necked flask equipped with a stirring apparatus, a cooling tube, a nitrogen gas introduction tube, a thermometer, a dropping funnel, and two, and heated to 85 ° C under a nitrogen gas atmosphere. A mixed solution of 480 g of polyoxyethylene monomethyl ether methacrylate (g) obtained in Example 7 and 200 g of toluene and a solution of 20 g of azobisisobutyronitrile dissolved in 100 g of toluene were put into a separate dropping funnel, respectively. It was dripped over 2 hours at 85-95 degreeC under nitrogen gas atmosphere, and after completion | finish of dripping, it was made to react for 1 hour in the same temperature range. After completion | finish of reaction, toluene which is a solvent was removed under 90-100 degreeC and pressure reduction, and the reddish brown copolymer (P-g) was obtained. The kinematic viscosity at 100 ° C of the obtained copolymer was 206 cSt, and the molecular weight determined by GPC was 19,700.

Example  18

200 g of ion-exchanged water and 100 g of 2-propanol were put into a 3-liter four-necked flask equipped with a stirring device, a cooling tube, a nitrogen gas introduction tube, a thermometer, and two dropping funnels, and the temperature was raised to 80 ° C. A mixed solution of 414 g of polyoxyethyleneoxypropylene monomethyl ether acrylate (j) obtained in Example 10, 29 g of acrylic acid, 200 g of ion-exchanged water, and 100 g of 2-propanol, and 20 g of a 10 wt% aqueous solution of ammonium persulfate were separately separately. The mixture was placed in a dropping funnel, and added dropwise in a nitrogen gas atmosphere at 80 to 90 ° C. for 3 hours. After completion of the reaction, 2-propanol as a solvent was removed under reduced pressure, neutralized by addition of 5N aqueous sodium hydroxide solution, and water was adjusted by adding ion-exchanged water to obtain an aqueous solution of the copolymer (P-j). It was 59.6 weight% when the polymer concentration of the copolymer aqueous solution was calculated | required from the drying loss after 120 degreeC and 2 hours passed. The kinematic viscosity at 25 degrees C of the obtained copolymer aqueous solution was 172 cSt, and the molecular weight of the copolymer calculated | required by GPC was 30,300.

Example  19

200 g of ion-exchanged water was put into a 2-liter four-necked flask equipped with a stirring device, a cooling tube, a nitrogen gas introduction tube, a thermometer, and two dropping funnels, and the temperature was raised to 80 ° C. under a nitrogen gas atmosphere. A solution obtained by dissolving 604 g of polyoxyethylene monomethyl ether methacrylate (k) obtained in Example 11 and 39 g of methacrylic acid in 400 g of ion-exchanged water, 3 g of ammonium persulfate and 2 g of sodium metall sulfonate were dissolved in 40 g of ion-exchanged water. The prepared solution was put into a separate dropping funnel, respectively, and it was dripped at 80-85 degreeC under nitrogen gas atmosphere over 2 hours. After completion of the dropwise addition, the reaction was carried out for 1 hour at the same temperature range. 5N sodium hydroxide aqueous solution was added, it neutralized, ion-exchange water was added, moisture was adjusted, and the aqueous solution of copolymer (P-k) was obtained. It was 59.2 weight% when the polymer concentration of the copolymer aqueous solution was calculated | required from the drying loss after 120 degreeC and 2 hours passed. The kinematic viscosity at 25 degrees C of the obtained copolymer aqueous solution was 397 cSt, and the molecular weight of the copolymer calculated | required by GPC was 36,200.

Comparative example  8

The reaction was carried out in the same manner as in Example 17, except that the polyoxyethylene monomethyl ether methacrylate (g ') obtained in Comparative Example 3 was used instead of the polyoxyethylene monomethyl ether methacrylate (g) obtained in Example 7. It carried out and obtained red-brown copolymer (P-g '). The kinematic viscosity at 100 ° C of the obtained copolymer (P-g ') was 243 cSt, and the molecular weight determined by GPC was 22,100.

Comparative example  9

The reaction was performed in the same manner as in Example 19 except that the polyoxyethylene monomethyl ether methacrylate (k ') obtained in Comparative Example 4 was used instead of the polyoxyethylene monomethyl ether methacrylate (k) obtained in Example 11. It carried out and obtained the aqueous solution of the copolymer (P-k '). It was 59.4 weight% when the polymer concentration of the copolymer aqueous solution was calculated | required from the drying loss after 120 degreeC and 2 hours passed. The kinematic viscosity at 25 degrees C of the obtained copolymer aqueous solution was 448 cSt, and the molecular weight of the copolymer calculated | required by GPC was 42,800.

Table 6 shows the compositions of the copolymers obtained in Examples 17-19 and Comparative Examples 8-9.

Copolymer symbol Compound of formula [2] Copolymerizable Monomer sign confiscation compound confiscation Example 17 P-g g 0.54 Maleic anhydride 0.55 Example 18 P-j j 0.20 Acrylic acid 0.40 Example 19 P-k k 0.20 Sodium Methacrylic Acid 0.45 0.01 Comparative Example 8 P-g ' g ' 0.54 Maleic acid 0.55 Comparative Example 9 P-k ' k ' 0.20 Sodium Methacrylic Acid 0.45 0.01

Example 20 (Evaluation in Toluene System as Dispersant for Inorganic Powder)

To a 300 ml beaker, 70 g of tar [Japan, Kanto Chemical Co., Ltd., 40000-02] and 90 g of toluene were added, and 0.14 g of the copolymer (Pa) obtained in Example 12 was added as a dispersant, Shuffled for a minute.

The prepared slurry-like composition was placed in a cylindrical pipe made of vinyl chloride having an inner diameter of 5 mm, an outer diameter of 60 mm, and a height of 40 mm placed on a glass plate, and the top surface was evenly flattened with a paste knife, and only the cylindrical pipe was gently drawn upwards. After the flow of the slurry composition was stopped, the maximum and minimum diameters of the spread composition were visually judged, and the length was measured in mm. The average of the largest diameter and the smallest diameter was calculated | required, and it represented by the integer of the unknown number which uses mm as a unit, and made it the flow value of a slurry composition. As a result, the flow was 155.

Example  21

A slurry-like composition was prepared in the same manner as in Example 20 except that the copolymer (Pd) obtained in Example 14 was used instead of the copolymer (Pa), and the flow value thereof was 162. Comparative Example 10

Except not adding a dispersing agent, it carried out similarly to Example 20, the slurry composition was prepared, and the floc was calculated | required and it was 83.

Comparative example  11

In the same manner as in Example 20, except that the copolymer (P-a ') obtained in Comparative Example 5 was used instead of the copolymer (P-a), a slurry composition was prepared and the flow value thereof was 126.

The results of Examples 20 to 21 and Comparative Examples 10 to 11 are shown in Table 7.

From the results in Table 7, the slurry compositions of Examples 20 and 21, in which the copolymer of the polymerizable polyoxyalkylene monoalkyl ether derivative of the present invention was added, had a large flow value and had a good dispersibility of tar. Able to know. On the other hand, the slurry composition of the comparative example 10 which does not add a dispersing agent, and the slurry composition of the comparative example 11 which added the copolymer obtained by the comparative example 5 also have a small float, and are inferior to the dispersibility of tar.

Example 22 (Evaluation in Ethylene Glycol Monobutyl Ether System as Dispersant for Inorganic Powder)

50 g of titanium oxide [Kanto Chemical Co., Ltd.] and 90 g of ethylene glycol monobutyl ether were added to a 300 ml beaker, and 0.5 g of 40 wt% aqueous solution of the copolymer (Pg) obtained in Example 17 was added as a dispersant. The mixture was stirred for 3 minutes with a stirring blade to prepare a slurry composition.

The prepared slurry-like composition was placed in a cylindrical pipe made of vinyl chloride resin having an inner diameter of 50 mm, an outer diameter of 60 mm, and a height of 40 mm placed on a glass plate, and the top surface was evenly flattened with a paste knife, and the cylindrical pipe was gently drawn upwards. After the flow of the slurry composition was stopped, the maximum and minimum diameters of the spread composition were visually judged, and the length was measured in mm. The average of the largest diameter and the smallest diameter was calculated | required, and it represented by the integer of the unknown number which uses mm as a unit, and made it the flow value of a slurry composition. As a result, Flotch was 141.

Example  23

A slurry-like composition was prepared in the same manner as in Example 22 except that 0.5 g of the aqueous solution of the copolymer (Pj) obtained in Example 18 was used instead of 0.5 g of the 40 wt% aqueous solution of the copolymer (Pg), and the flo I asked for Chi, which was 137.

Comparative example  12

Except not adding a dispersing agent, it carried out similarly to Example 22, the slurry composition was prepared, and the floc was calculated | required and it was 77.

Comparative example  13

A slurry-like composition was prepared in the same manner as in Example 22 except that a 40% by weight aqueous solution of the copolymer (P-g ') obtained in Comparative Example 8 was used instead of a 40% by weight aqueous solution of the copolymer (Pg). It was 118.

The results of Examples 22 to 23 and Comparative Examples 12 to 13 are shown in Table 8.

From the results in Table 8, the slurry compositions of Examples 22 and 23, in which the copolymer of the polymerizable polyoxyalkylene monoalkyl ether derivative of the present invention was added, had a large float and had good dispersibility of titanium oxide. Able to know. On the other hand, the slurry composition of the comparative example 12 which does not add a dispersing agent, and the slurry composition of the comparative example 13 which added the copolymer obtained by the comparative example 8 also have a small float, and are inferior to the dispersibility of titanium oxide.

Example  24

In a dough bowl of a dough kneader for kneading in accordance with JIS R 5201, weighing 600 g of ordinary Portland cement and 1,025 g of sand [Japan, Chiba 켕 Kimmitsu, dry weight ratio 2.51, surface yield 0.2% by weight], The dough was mixed for 30 seconds at low speed. Next, water was added to 2.4 g of the copolymer (Pa) obtained in Example 12 and 0.1 g of an antifoaming agent (Japan, Nihon Yushi Co., Ltd., Disform CC-118). The dough was mixed at low speed for 15 seconds, and kneaded at high speed for 2 minutes to prepare mortar.

About the prepared mortar, the flow value of mortar was measured based on the flow test of JISR5201 base material, and it was 251. The mortar after the flow measurement was stored in an airtight container, and the flow test was repeated for 30 minutes and 60 minutes after the start of kneading. The floc after 30 minutes was 234, and the floc after 60 minutes was 182.

Example  25

Instead of 2.4 g of copolymer (P-a), the flow value of mortar was measured in the same manner as in Example 24 except that 4.76 g of an aqueous solution of the copolymer (P-b) obtained in Example 13 was used.

The mortar of mortar was 268 immediately after preparation, 265 after 30 minutes, and 210 after 60 minutes.

Comparative example  14

Floating value of mortar was measured like Example 24 except having used the copolymer (P-a ') obtained by the comparative example 5 instead of the copolymer (P-a).

The mortar of mortar was 154 immediately after preparation, 117 after 30 minutes, and 110 after 60 minutes.

Comparative example  15

Floating value of mortar was measured like Example 24 except having replaced 4.7 g of aqueous solutions of the copolymer (P-b ') obtained by the comparative example 6 instead of 2.4 g of copolymers (P-a).

The mortar of mortar was 196 immediately after preparation, 30 minutes after 183, and 143 after 60 minutes.

Example  26

In the same manner as in Example 24, except that the copolymer (P-g) obtained in Example 17 was used instead of the copolymer (P-a), the flow value of mortar was measured.

The mortar of mortar was 240 immediately after adjustment, 221 after 30 minutes, and 177 after 60 minutes.

Example  27

Instead of 2.4 g of copolymer (P-a), the flow value of mortar was measured in the same manner as in Example 24 except that 6.0 g of an aqueous solution of the copolymer (P-k) obtained in Example 19 was used.

The mortar of mortar was 229 immediately after preparation, 30 minutes after 213, and 60 minutes after 188.

Comparative example  16

In the same manner as in Example 24, except that the copolymer (P-g ') obtained in Comparative Example 8 was used instead of the copolymer (P-a), the flow value of mortar was measured.

The mortar of mortar was 196 immediately after preparation, 149 after 30 minutes, and 130 after 60 minutes.

Comparative example  17

Instead of 2.4 g of copolymer (P-a), the flow value of mortar was measured in the same manner as in Example 24 except that 6.0 g of an aqueous solution of the copolymer (P-k ') obtained in Comparative Example 9 was used.

The mortar of the mortar was 141 immediately after dispensing, 123 after 30 minutes, and 104 after 60 minutes.

Tables 9 show the results of Examples 24-27 and Comparative Examples 14-17.

From the results of Table 9, the mortars of Examples 24, 25, 26 and 27 to which a dispersant containing a copolymer of the polymerizable polyoxyalkylene monoalkyl ether derivative of the present invention was added were immediately after the dough was completed. After 30 minutes and after 60 minutes, the flow is large and it is seen that the dispersibility is good. On the other hand, as for the mortar of the comparative example 14, the comparative example 15, the comparative example 16, and the comparative example 17 which added the dispersing agent containing the copolymer obtained in the comparative example 5, the comparative example 6, the comparative example 8, and the comparative example 9, all the flocs were It is small and is inferior in dispersibility.

Polymeric polyoxyalkylene monoalkyl ether derivatives based on polyoxyalkylene monoalkyl ethers having a specific molecular weight distribution of the present invention have very little by-products of bifunction, and polymers using these as monomers are useful for crosslinking. Since there is little harmful effect, when used as a dispersant for various powders such as inorganic pigments and organic pigments, since it shows excellent dispersibility in a small amount of addition, even when used as an additive for civil construction cement, Excellent fluidity is displayed in a small amount, which improves workability and workability.

Claims (5)

Formula [1]: R ¹ O (AO) n H ...... [1] (Wherein R ¹ is a hydrocarbon group of ¹ to 18 carbon atoms, AO is an oxyalkylene group of 2 to 4 carbon atoms, AO is at least one species, and when AO is at least two species, the additional form thereof is in a random shape) Or in the form of a block, n is from 5 to 500 in terms of the average molar number of the oxyalkylene group), and SHODEX GPC SYSTEM-11 as a GPC system and SHODEX RI-71 as a differential refraction system. Three continuous SHODEX KF804Ls were used as a column, the column temperature was 40 ° C, and tetrahydrofuran was used as the developing solvent, and the sample solution 0.1 mL / min of the developing solvent was used at a flow rate of 0.1% by weight. In gel permeation chromatography obtained by injecting ml, the start point of elution when the maximum refractive index intensity maximum on the chromatogram expressed by the refractive index intensity and the elution time obtained using the differential refractive index meter and the shortest distance of the baseline are L. Ugh To the refractive index from the intensity of the chromatogram L / 3 to the peak area of the fastest eluting time for the S ₁ and the elution of the refractive index up to the maximum point strength of the peak area from the start point S ₀ ratio of formula (A): S ₁ / S ₀ ≤0.15 ..... (A) The following formula [2] or formula [3], wherein the polyoxyalkylene monoalkyl ether represented by the formula [1] satisfying the following is used as a raw material: R ¹ O (AO) nR ² ...... [2] R ¹ O (AO) nR ³ ......... [3] (Wherein, R ¹ , AO and n have the meaning as defined in the formula [1], R ² is an unsaturated hydrocarbon group of 3 to 4 carbon atoms, R ³ is acryloyl group or meta A polymerizable polyoxyalkylene monoalkyl ether derivative represented by the above). Formula [1]: R ¹ O (AO) n H ...... [1] (Wherein R ¹ is a hydrocarbon group of ¹ to 18 carbon atoms, AO is an oxyalkylene group of 2 to 4 carbon atoms, AO is at least one species, and when AO is at least two species, the additional form thereof is in a random shape) Or in the form of a block, n is from 5 to 500 in terms of the average molar number of the oxyalkylene group), and SHODEX GPC SYSTEM-11 as a GPC system and SHODEX RI-71 as a differential refraction system. Three continuous SHODEX KF804Ls were used as a column, the column temperature was 40 ° C, and tetrahydrofuran was used as the developing solvent, and the sample solution 0.1 mL / min of the developing solvent was used at a flow rate of 0.1% by weight. In gel permeation chromatography obtained by injecting ml, the start point of elution when the maximum refractive index intensity maximum on the chromatogram expressed by the refractive index intensity and the elution time obtained using the differential refractive index meter and the shortest distance of the baseline are L. Ugh To the refractive index from the intensity of the chromatogram L / 3 to the peak area of the fastest eluting time for the S ₁ and the elution of the refractive index up to the maximum point strength of the peak area from the start point S ₀ ratio of formula (A): S ₁ / S ₀ ≤0.15 ..... (A) When the polyoxyalkylene monoalkyl ether represented by the formula [1] satisfying the above is prepared by addition polymerization of a C 2 to C 4 alkylene oxide to a monohydric alcohol, moisture in a reaction vessel having a volume of V (ml) When the solvent Wi (g) of Ci (ppm) was added and the solvent was washed after stirring, the water content of the solvent removed was Cf (ppm), and the following formula (B): Moisture in Reaction Vessel = Wi × (Cf-Ci) / V≤10 ...... (B) By adjusting the water in the reaction vessel to obtain a polyoxyalkylene monoalkyl ether represented by the formula [1], the polyoxyalkylene monoalkyl ether represented by the obtained formula [1] is used as a raw material. By etherifying the polyoxyalkylene monoalkyl ether represented by formula [1], the polymerizable polyoxyalkylene monoalkyl ether derivative represented by the following formula [2] is obtained or the polyoxy represented by the formula [1] A method for producing a polymerizable polyoxyalkylene monoalkyl ether derivative characterized by obtaining an polymerizable polyoxyalkylene monoalkyl ether derivative represented by the following formula [3] by esterifying an alkylene monoalkyl ether: R ¹ O (AO) nR ² ...... [2] R ¹ O (AO) nR ³ ...... [3] (Wherein, R ¹ , AO and n have the meaning as defined in the formula [1], R ² is an unsaturated hydrocarbon group of 3 to 4 carbon atoms, R ³ is acryloyl group or meta Chlorophyll). The compound according to claim 1, wherein the polymerizable polyoxyalkylene monoalkyl ether derivative is formula [2]: R ¹ O (AO) nR ² ...... [2] Wherein R ¹ , AO and n have the same meanings as defined in the above formula [1], and R ² is an unsaturated hydrocarbon group having 3 to 4 carbon atoms. Polyoxyalkylene monoalkyl ether derivatives. The method according to claim 1, wherein the polymerizable polyoxyalkylene monoalkyl ether derivative is represented by the following formula [3]: R ¹ O (AO) nR ³ ......... [3] Wherein R ¹ , AO and n have the same meanings as defined in the formula [1], and R ³ is an acryloyl group or a methacryloyl group. Sex polyoxyalkylene monoalkyl ether derivatives. delete

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